Composite particles, compositions and methods

ABSTRACT

Composite particulates, topical composition containing composite particulates, methods for improving the appearance of skin depth, dimensionality or undertones; a method for improving the ashy, chalky or mask-like appearance of color cosmetic compositions on the skin; and a method for reducing the number of shades in a color cosmetic shade range by formulating the cosmetic with composite particulates.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a national stage filing of PCT/US2011/020248, filedJan. 5, 2011, which claims priority of U.S. Provisional Application No.61/296,348, filed Jan. 19, 2010 and U.S. Provisional Application No.61/357,809, filed Jun. 23, 2010.

TECHNICAL FIELD

The invention is in the field of particulates and their use in cosmeticcompositions with improved visual appearance on keratinous surfaces.

BACKGROUND OF THE INVENTION

A high percentage of women use foundation makeup. Current commercialproducts are of excellent quality and are available in shades thatcorrectly match skin color. Yet foundation users remain unsatisfied. Forexample, a high percentage of ethnic women use foundation, yet areunhappy with the ashy, chalky tone that it often gives their skin. Oftenthese products contain significant amounts of titanium dioxide whichprovides excellent coverage but can create a mask-like appearance. Thisis believed to be due in part to the undertones in skin color whichprovide the appearance of warmth or coolness in addition to depth anddimension. Foundation makeup that masks the natural undertones of skinoften causes the facial skin to appear unnatural because it covers thenatural dimensionality of the skin. The big need gap is for makeupproducts such as foundations that provide coverage without masking skinundertones, which provides an undesirable mask-like appearance.

Another reason for the importance of formulating such foundations has todo with SKU (“stock keeping unit”) reduction. In order to meet the needsof all users, cosmetics companies must formulate a large number offoundation color choices to satisfy their customer base. Many of theseshades sell very poorly or not at all. A large number of SKUs meanslarger cost to the cosmetics manufacturer. Thus, there is interest informulating foundation makeup products that will match a wider range ofskin colors. SKU reduction benefits both the cosmetics company and theconsumer. In addition it removes some of the confusion associated withthe consumer's color choices, which are never easy. Also more SKU'smeans increased product cost to the consumer because, ultimately, thehigher cost of goods is reflected in a higher retail price to consumers.

It has been found that when color cosmetics are formulated with certaintypes of composite particulates that have a portion of clear ortranslucent thermoplastic material in the particulate, that colorcosmetics will exhibit improved appearance on skin, including animproved appearance of dimensionality, depth and skin undertones, aswell as reduction in the ashy, chalky, or mask-like appearance of colorcosmetics such as foundation. In addition, the composite particulatesfacilitate reduction in the number of shades of the color cosmetic thatare necessary to match all skin shades in a shade range.

It is the object of the invention to provide color cosmetic compositionsthat are more “universal”, meaning that a particular color will match alarger number of color shades in a shade category. For example, afoundation that may be deemed more universal in its color matchingproperties may be designated Color #1 and it may match skin color shades1, 2 and 3 in the shade category “Light” as opposed to the necessity ofthree different shades in the Light category with a traditionalfoundation.

It is a further object of the invention to provide a compositeparticulate containing a colorant portion and a clear or translucentthermoplastic portion.

It is a further object of the invention to provide a composition forapplication to keratinous surfaces such as skin, hair, or nails,comprising the composite particulate.

It is a further object to provide a method for improving the appearanceof depth, dimensionality, and skin undertones by providing a naturalappearance color cosmetic that contains composite particulates.

It is a further object of the invention to provide a method for reducingthe ashy, chalky, or mask-like appearance of compositions such asfoundation makeup on the skin by formulating the composition withcomposite particulates.

It is a further object of the invention to provide a method for reducingthe number of SKUs in a color cosmetic shade range by formulating thecolor cosmetics with composite particulates.

SUMMARY OF THE INVENTION

The invention is directed to a composition for application to keratinoussurfaces containing composite particulates in the fused agglomerate formhaving a portion comprised of at least one colorant and a portioncomprised of at least one clear or translucent thermoplastic material,wherein the composite particulates contain, by weight of the totalcomposite particulate, from about 1 to 99.9 parts of the colorantportion and from about 0.1 to 100 parts of the clear or translucentthermoplastic material portion, and wherein at least some of thecomposite particulates present in the composition have a colorantportion present.

The invention is further directed to a composite particulate in thefused agglomerate form having a portion comprised of at least onecolorant and a portion comprised of at least one clear or translucentthermoplastic material, wherein the composite particulates contain, byweight of the total composite particulate, from about 1 to 99.9 parts ofthe colorant portion and from about 0.1 to 100 parts of the clear ortranslucent thermoplastic material portion, and wherein at least some ofthe thermoplastic material in the particulate is in the form of solid orhollow partial or complete spheres.

The invention is also directed to a method for imparting color to skinwhile improving the appearance of skin dimensionality, depth, orundertones by application of a composition comprising compositeparticulates having a portion comprised of at least one colorant and aportion comprised of at least one clear or translucent thermoplasticmaterial.

A method for reducing the ashy, chalky, or mask-like effect of a colorcosmetic composition on skin comprising substituting 0.1 to 99%,preferably 10-90% of the total colorant component present in thecomposition with composite particulates having a portion comprised of atleast one colorant and a portion comprised of at least one clear ortranslucent thermoplastic material, wherein the composite particulatescontain, by weight of the total composite particulate, from about 1 to99.9 parts of the colorant portion and from about 0.1 to 100 parts ofthe clear or translucent thermoplastic material portion.

A method for reducing the number of SKUs in a shade range for a cosmeticproduct comprising providing a cosmetic product wherein from about0.1-99%, preferably 10-90% by weight of the total colorant componentcomprises composite particulates.

DETAILED DESCRIPTION I. Description of the Drawings

FIG. 1: Depicts types of composite particulates that may be used in thecompositions and methods of the invention where the clear area withinthe black lines depicts the clear thermoplastic material portion of thecomposite particulate and the solid black portion depicts the colorantportion of the composite particulate.

1(A): is a composite particulate in the fused agglomerate form where thethermoplastic material is in the form of hollow or solid spheres, suchthat when such spheres are reacted with the solvent and colorant to formthe composite particulate, at least some of the thermoplastic materialportion remains in the form of entire or partial spheres.

1(B): is a composite particulate in the encapsulated form where thecolorant portions are encapsulated within the thermoplastic materialportion and where the composite particulate is generally spherical inshape.

1(C): is a composite particulate in encapsulated form having anon-spherical shape—depicted as substantially octagonal—and wherein thecolorant portion is an irregular deposit embedded within thethermoplastic material portion.

1(D): is a composite particulate in the encapsulated form having airregular shape and having the colorant portion encapsulated within.

FIG. 2: Depicts a composite particulate in the form of a collapsedmicrosphere. The larger sphere depicts an untreated clear or translucenthollow microsphere with a deformable polymeric shell and an expandablefluid entrapped therein. The smaller sphere on the right depicts acollapsed polymeric shell with solid colorant particles trapped withinand a liquid impermeable coating.

FIG. 3: is a chart that shows the reduction in foundation makeup colorSKUs achieved with foundation formulas made with the composite particlesof the invention (11 shades matched all skin colors) when compared withthe shade palette of MAC Studio Fix Fluid SPF15 (19 shades necessary tomatch all skin colors). Thus, a 42% reduction (8 shades) in SKUs.

II. Definitions

In the terms used herein the singular shall include the plural and viceversa.

All percentages mentioned herein are percentages by weight unlessotherwise indicated.

The term “agglomerate” means, when referred to the compositeparticulate, a cluster of colorants and the clear thermoplastic materialwhere the clusters are fused, e.g. chemically or physically bondedtogether.

The term “ashy” or “chalky” means the whitish, ash-like appearance thatcosmetics such as foundation may exhibit on skins, particularly darkerskins.

The term “clear” means the same as “transparent” and that thethermoplastic material permits both the passage of light and issufficiently free of cloudiness or haziness to provide a clear view ofwhat lies behind. In some cases the thermoplastic materials used in thecompositions and methods of the invention may be individually be in theclear particulate or spherical particulate form, yet when viewed in bulkthey may exhibit a whitish or grayish powder appearance. In this case itis the appearance of the individual particulate that governs.

The term “collapsed microsphere” means an originally hollow microspherethat, during the manufacturing process, has formed channels andinterstices into which colorants are entrapped within and dispersedthroughout. Each individual microsphere with the dispersed and trappedcolorants forms its own closed system. In contrast, in fusedagglomerates the colorant deposit is found in agglomerates that arefused with agglomerates formed from the clear thermoplastic material.

The term “colorant” when used herein means colored pigments, ornon-colored or white particulates that are sometimes used as fillers orto mute color in cosmetic compositions. In general the term “colorant”excludes clear or translucent thermoplastic materials in the form ofparticulates.

The term “colorant component” means the total amount of the colorants asdescribed in section II below that are present in the composition.

The term “composite particulate” means a solid particle that contains aportion comprised of at least one colorant and a portion comprised of atleast one clear or translucent thermoplastic material wherein the twoportions are fused together, e.g. not present as a simple unreactedmixture.

The term “encapsulated particulate” means a type of compositeparticulate where the colorant component is encapsulated within theclear thermoplastic material.

The term “fused agglomerate” means with respect to the compositeparticulate, that it is an agglomeration of colorant and clear ortranslucent thermoplastic material where the agglomerates are fused,e.g. chemically bound, to each other. In the case where the clearthermoplastic portion of the fused agglomerate is in the form of hollowor solid spherical particles, the fused agglomerate may contain athermoplastic portion comprising agglomerated partial or entire solid orhollow spheres.

The term “mask-like” means the appearance of a color cosmeticcomposition such as foundation on the facial skin when the compositionmasks skin undertones to a degree sufficient to provide a visuallyunnatural appearance.

The term “room temperature” means a temperature of about 25° C.

The term “SKU” means stock keeping unit, which is the lowest level ofproduct detail. SKU numbers are generally in the format xxxx-xx wherethe first four numbers designate the product name and, for colorcosmetics, the last two numbers the shade code. For example a SKU numberof 1234-56 means, for example, that foundation makeup product line “x”is designated by the number 1234, and the numbers “56” refer to oneparticular shade of the foundation makeup.

The term “translucent” means, with respect to the thermoplasticmaterial, that it permits passage of light but has sufficient cloudinessor haziness to prevent a clear view of what lies behind. In cases wherethe thermoplastic material is in the individual particulate form theparticles may be translucent, but when viewed in the bulk form suchtranslucent particles may appear as a whitish or grayish powder. In thiscase it is the appearance of the individual particles that governs.

II. The Composite Particulate

A. Description

The composite particulate may be in the form of an agglomerate,preferably a fused agglomerate, a collapsed microsphere, or anencapsulated particulate.

When the composite particulate is in the form of a fused agglomerate, itis generally made by blending a mixture of one or more colorants and oneor more clear or translucent thermoplastic synthetic or naturalpolymeric materials to create a composite that retains properties ofboth the colorant and the thermoplastic material. Preferably thecolorants and the clear or translucent thermoplastic material used tomake the composite particulate are in particulate form.

The composite particulate is solid at room temperature and has aparticle size ranging from about 0.01 to 200, preferably from about 0.1to 150, more preferably from about 1 to 100 microns in diameter. Thecomposite particulate may have a variety of shapes including sphericalor other types of irregular shapes. The composite particulate preferablycontains a colorant portion ranging from about 0.1 to 99%, preferablyfrom about 0.5 to 90%, more preferably from about 5-80%; and clear ortranslucent thermoplastic portion ranging from about 0.1 to 100%,preferably from about 0.5 to 90%, more preferably from about 5 to 80%,all percentages by weight of the total composite particulate.

B. Components of the Composite Particulate

1. Colorants

Colorants suitable for use in making the composite particulate includeorganic pigments, which are generally referred to as D&C and FD&C colorssuch as blues, browns, greens, oranges, reds, yellows, etc. Such organicpigments may also include insoluble metallic salts of certified coloradditives, referred to as D&C Lakes or FD&C Lakes.

Suitable colorants also include inorganic pigments such as iron oxides,ultramarines, chromium, chromium hydroxide colors, and mixtures thereof.Iron oxides of red, blue, yellow, brown, black, and mixtures thereof aresuitable.

Further examples of suitable colorants include colored or non-colored(for example white) non-pigmented powders. Examples include non-clear ortranslucent particulates such as bismuth oxychloride, titanated mica,fumed silica, spherical silica, polymethylmethacrylate, micronizedteflon, boron nitride, acrylate copolymers, aluminum silicate, aluminumstarch octenylsuccinate, bentonite, calcium silicate, cellulose, chalk,corn starch, diatomaceous earth, fuller's earth, glyceryl starch,hectorite, hydrated silica, kaolin, magnesium aluminum silicate,magnesium trisilicate, maltodextrin, montmorillonite, microcrystallinecellulose, rice starch, silica, talc, mica, titanium dioxide, zinclaurate, zinc myristate, zinc rosinate, alumina, attapulgite, calciumcarbonate, calcium silicate, dextran, kaolin, nylon, silica silylate,silk powder, sericite, soy flour, tin oxide, titanium hydroxide,trimagnesium phosphate, walnut shell powder, or mixtures thereof.

Preferred colorants have a particle size ranging from about 0.001 to 150microns, preferably from about 0.005 to 100 microns, more preferablyfrom about 0.1 to 50 microns.

2. Clear or Translucent Thermoplastic Material

The clear or translucent thermoplastic material is preferably asynthetic polymer. Generally, in order to provide the desired clarity ortranslucence the index of refraction of the polymer material used toprepare the composite ranges from about 1.3 to 1.8, or 1.4 to 1.6. Inaddition, the clear or translucent polymer is generally a solid at roomtemperature, and may have a density ranging from about 0.5 to 5grams/cm³. The polymer preferably has a melting point ranging from about50° to 200° C.

The material used to prepare the composite may be in the form of hollowor solid spheres. Or it may be in the form of a solid block or filmwhich may be ground to form particulates of varying sizes and shapes. Inone preferred embodiment of the invention the clear or translucentthermoplastic material is in the form of particulates, which may behollow or solid spherical particulates; preferably having particle sizeranging from about 0.01 to 150 microns, more preferably from 0.1 to 100microns, even more preferably from 0.5 to 75 microns.

Suitable polymers for making the clear or translucent thermoplasticmaterial used in the manufacture of the composite particulate include,but are not limited to those set forth herein.

(a). Homo- or Copolymers of Ethylenically Unsaturated Monomers

(i). Acrylic Acid, Methacrylic Acid or Their Simple Esters

Suitable polymers include homo- or copolymers from ethylenicallyunsaturated monomers such as acrylic acid, methacrylic acid, or theirsimple C₁₋₂₀ aliphatic or aromatic esters. Examples of such monomersinclude methyl acrylate, methyl methacrylate, acrylate, ethyl acrylate,ethyl methacrylate, butyl acrylate, butyl methacrylate, hexyl acrylate,hexyl methacrylate, and so on.

It is possible for the polymer to be uncrosslinked or partiallycrosslinked. If crosslinked, divinyl crosslinking agents in the form ofalpha omega dienes may be suitable, for example those having 2 to 10carbon atoms. Examples include ethene, propylene, butene and so on. Ifthe polymer is crosslinked it is believed that when it is contacted withthe solvent the polymer will tend to swell rather than completelysolvate. If the polymer was in the form of spherical particulates, thiswill result in a final composite particle where the thermoplasticportion that is present may contain either partial or complete spheres.It is believed that when the composite particulate contains sphereportions this contributes to the unique visual effect provided by thecomposite particulate.

One preferred polymer is polymethylmethacrylate (PMMA) in spherical formhaving a specific gravity ranging from about 1.100 to 1.250 gm/ml, aparticle size ranging from about 4.5 to 8.5 microns, and density rangingfrom 1 to 1.5 gm/cm³. Such a particle may be purchased from SEPPICCorporation under the trade name Sepimat P or from Tomen American underthe trade mark Microsphere M-100.

Other types include styrenated acrylates (copolymers of styrene andacrylic acid, methacrylic acid or their simple C1-10 esters); styreneacrylonitrile (“SAN”) polymers, acrylonitrile butadiene styrenecopolymers (“ABS”).

(ii). Homo- or Copolymers of Alkenes

Also suitable are homo- or copolymers of C2-10 alkenes such aspolyethylene, polypropylene, polybutene, and the like which may also becrosslinked. One suitable alkene is an uncrosslinked ethylenehomopolymer sold under the trade name Performalene 400® which is a highmolecular weight polyethylene homopolymer sold by Baker Hughes.

(b). Polycarbonates

Also suitable as thermoplastic material used to make the composite arevarious types of polycarbonates. The term “polycarbonate” means polymershaving functional groups linked together by carbonate (—O—C(O)—O—)groups, and they may be polyaromatic carbonates or polyaliphaticcarbonates. The polycarbonates may be in the form of solid or hollowspherical particles, ground particulates, or in a film or block form.

3. Solvents

Suitable solvents for swelling or solvating the clear or translucentthermoplastic material can be determined by ascertaining theirHildebrand Solubility Parameter which is the square root of the cohesiveenergy density of the solvent. The formula for the Hildebrand SolubilityParameter (δ) is:δ=√{square root over (((Hv−RT)/Vm)}

-   -   expressed in (calories/cm³)^(1/2)    -   wherein:        -   H_(v)=the heat of vaporization        -   R=the gas constant        -   T=temperature        -   V_(m)=molar volume.

One type of solvent suitable for use in preparing the compositeparticulate may be identified by its Hildebrand Solubility Parameter. Inthis case, solvents having a Hildebrand Solubility Parameter rangingfrom about 1 to 16, more particularly 3-15, more preferably 5-10(calories/cm³)^(1/2) may be good solvents for use in preparing thecomposite particulate.

Identification of suitable solvents for the thermoplastic materialsselected may also be determined by the procedures set forth in “A SimpleSolvent Selection Method for Accelerated Solvent Extraction of Additivesfrom Polymers”, Analyst, Volume 124, pages 1707-1710—The Royal Societyof Chemistry, 1999, hereby incorporated by reference in its entirety.

Other types of preferred solvents include aliphatic, aromatic, orheterocyclic, saturated or unsaturated hydrocarbon chains ranging fromabout 1 to 12, preferably from about 1 to 10 carbon atoms, morepreferably from about 2 to 8 carbons. Such carbon chains may have one ormore carbonyl, hydroxyl, amine, halogen, ether linkages, or amide groupssubstituted on the hydrocarbon chain. Examples of such solvents includeacetone, xylene, methylethyl ketone (MEK), dimethylformamide,dimethylchloride, trichloroethylene, trichloromethane, methanol,ethanol, isopropanol, ethyl acetate, butyl acetate, toluene, benzene,cyclohexane, amyl acetate, carbon tetrachloride, toluene,tetrahydrofuran, benzene, diacetone alcohol, ethylene dichloride,methylene chloride, DMSO, morpholine, cellosolve, pyridine, propanol; orC₁₋₄ mono- or dialkyl ethers of ethylene glycol, and the like. Mostpreferred are ethanol, acetone, xylene, or MEK. Most preferred isacetone.

C. How to Make

The composite particulate in the fused agglomerate form may be made bycombining the thermoplastic material and colorant then mixing with anamount of solvent sufficient to cause the thermoplastic material toswell (e.g. expand) or solvate. The ratio of thermoplastic material tocolorant to solvent may be determined by ascertaining the particularthermoplastic material, the amount in which it is present, and whatsolvent would be most appropriate for swelling or solvating thethermoplastic material. Generally, suitable ratios of colorant tothermoplastic material to solvent may range from about 0.1-50 partscolorant to 0.1 to 100 parts thermoplastic material to 0.1 to 100 partssolvent. Preferably the process is conducted at room temperature,although, if desired, heat may be applied. The colorant, solvent, andthermoplastic material are combined for a time sufficient to permit thesolvent to swell or solvate the thermoplastic material. The amount oftime may range from 1 to 72 hours, or from 10 to 50 hours. After theappropriate time period the mixture is removed from the vessel andspread into a glass baking dish to form a flat surface, then allowed todry for 12 to 72 hours, preferably from 24 to 48 hours, or untilhardened. The hardened mixture is then removed from the dish and brokenup with the hands into smaller pieces. The resulting pieces aresubjected to various procedures such as milling and sieving to achievecomposite particulates having the desired shape and size.

The colorant portion and thermoplastic material portion of the compositeparticulate are fused such that the entire composite is in a particulateform. In the preferred embodiment the composite particulate may appearas a fused agglomerate of the colorant component and the thermoplasticmaterial component, and wherein the latter will exhibit portions thatare in the solid or hollow partial spherical form; that is spheres thatwere swelled but not completely solvated in the manufacturing process.

If desired the composite particulates may be coated with variousmaterials to make them more hydrophilic or lipophilic as desired.Suitable coatings include, but are not limited to oils, structuringagents, and any one or more of the ingredients further listed herein asbeing suitable for use in cosmetic compositions of the invention.Further examples include silicone elastomers, silicone resins, siliconegums, synthetic or natural waxes, and the like. If the compositeparticulates are coated, the coating comprises, preferably, from about0.1 to 45%, more preferably from about 0.1 to 30%, most preferably fromabout 1 to 10% by weight of total composite particulate. Oneparticularly preferred coating is trisiloxane/dimethicone silylate.

D. Another Embodiment of the Composite Particle

Also suitable is a composite particle in the collapsed microsphere form.Such particulates are disclosed in U.S. Patent Publication No.2009/0155371, hereby incorporated by reference in its entirety. In thiscase the clear or translucent thermoplastic material is in the form of acollapsed microsphere having the colorant entrapped entirely within themicrosphere rather than forming a portion of an agglomerate. Thecollapsed microsphere may be optionally coated with a membrane orcoating in the same manner as set forth with the fused agglomerate formof the composite particulate. These composite particles in the form ofcollapsed microspheres may be formed by:

(a) forming a gelled mixture by mixing either simultaneously orsequentially in any order: (1) clear or translucent hollow microsphereshaving internal channels, preferably in the open cell form, that have adeformable polymeric shell having entrapped therein an expandable fluid,(2) a polar organic solvent capable of swelling but not dissolving thepolymeric shells of the hollow microspheres, and (3) colorants, whereinmicro-channels are formed in the swelled polymer shells to allow entryof the colorants into the hollow microspheres and exit of the expandablefluid therefrom, thereby forming microspheres that each comprises acollapsed polymeric shell in a gelled state and has one or more of saidcolorants entrapped therein;

(b) removing the expandable fluid and the polar organic solvent from thegelled mixture; and

(c) coating the microspheres with a film-forming material to form aliquid-impermeable coating thereon.

In the resulting collapsed microspheres the colorant particles areentrapped within the microspheres. In some cases the colorant that isused may be in the form of submicron particle sizes, in which case thecollapsed microspheres may have an average particle size that may be atleast 10 times, preferably 20 times, more preferably 50 times, and mostpreferably 100 times, larger than the average particle size of thecolorant particles used to make the composite particulate.

Entrapment of the pigment particles is achieved in the present inventionby first providing clear or translucent hollow microsphere that have adeformable polymeric shell and which may or may not have an expandablefluid within the hollow portion of the microsphere. The microspheres arethen mixed with, either sequentially in any order or simultaneously, apolar organic solvent capable of swelling but not dissolving thepolymeric shells of the hollow microspheres and solid particles to beentrapped. A gelled mixture is thereby formed, which containsmicrospheres with polymeric shells in a gelled state, which aresufficiently swelled so as to have micro-channels or through-holesformed therein to allow entry of the colorant particles into themicrospheres. Such micro-channels or through-holes in the swelledpolymeric shells of the microspheres also allow exit of the expandablefluid from the microspheres, thereby causing immediate collapse orimplosion of the polymeric shells and entrapping the colorant particlesinside the microspheres. Subsequently, the expandable fluid and thepolar organic solvent are removed from the gelled mixture. Preferablybut not necessarily, a film-forming material is coated over thecollapsed polymeric shells to form a liquid-impermeable membranethereon, which functions to isolate the collapsed polymeric shells ofthe microspheres from any solvent in the surrounding environment thatmay swell or otherwise affect the structural integrity of such polymericshells. In this manner, the solid particles can be securely entrappedinside the microspheres with little or no risk of leaking out.

The hollow microspheres used as the clear or translucent thermoplasticmaterial, as initially provided (i.e., before mixing with the solidparticles and the polar organic solvent) are preferably expandablehollow polymeric microspheres, each of which contains a deformablepolymeric shell that is gas-tight and has enclosed or encapsulatedtherein an expandable fluid. Upon heating, the enclosed or encapsulatedfluid can expand volumetrically to apply pressure on the interior wallof the deformable polymeric shell. At the same time, the elevatedtemperature may cause the polymeric shell to soften, thereby allowingthe entire microsphere to expand in a manner similar to a balloon.

The deformable polymeric shells of the hollow microspheres can be formedof any synthetic or natural crosslinked or un-crosslinked polymer. Ifthe polymer is crosslinked, it is preferred that it is weaklycrosslinked. Preferably, but not necessarily, the polymeric shells ofthe hollow microspheres comprise at least one synthetic polymer obtainedby polymerization of one or more ethylenically unsaturated monomers toform homopolymers or copolymers of ethylenically unsaturated monomers orcopolymers of ethylenically unsaturated monomers and one or more organicgroups. Examples of ethylenically unsaturated monomers that may besuitable include, for example, vinylidene chloride, vinyl chloride,acrylonitrile, acrylic acid and its corresponding C₁-C₂₀ aliphatic oraromatic esters, methacrylic acid and its corresponding C₁-C₂₀ aliphaticor aromatic esters, acrylamide, methacrylamide, vinyl pyrrolidone,alkenes such as styrene, ethylene, propylene, butylene, methylpentene,1,3-butadiene, and the like. The polymeric shells of the hollowmicrospheres may also be formed of suitable synthetic polymers, such aspolyesters, polyamides, polyphthalamides, polyimides, polycarbonates,polyketones, cellulose acetate, polysulfones, polyphenylene sulfides,polyphenylene oxides, polylactic acids, polyvinylpyrrolidone,polystyrene, polyacrylonitrile, polyacrylamide, polyacrylates, andcopolymers of the above-listed polymers. In a particularly preferredembodiment, the deformable polymeric shells of the hollow microspheresare formed of a copolymer of vinylidene chloride, acrylonitrile, and/ormethyl methyacrylate.

The expandable fluid inside the hollow microspheres of the presentinvention can be any suitable gas (e.g., air or nitrogen) or volatileliquid hydrocarbons (e.g., isobutane or isopentane). Preferably, theexpandable fluid is selected from the group consisting of air, nitrogen,isobutane, and isopentane. More preferably, the expandable fluid iseither isobutane or isopentane.

Hollow microspheres having deformable polymeric shells comprised of acopolymer of vinylidene chloride, acrylonitrile, and methylmethacrylatewith an expandable fluid comprised of isobutane or isopentane arecommercially available under the trade name of EXPANCEL® from Expancel,Inc. at Duluth, Ga. The EXPANCEL® hollow microspheres are available invarious forms, e.g., dry, wet, unexpanded or pre-expanded. Both the dry,unexpanded microspheres (EXPANCEL® DU) and the dry, expandedmicrospheres (EXPANCEL® DE) can be used in the present invention forentrapping and stabilizing the solid particles. The EXPANCEL® DUmicrospheres have an average particle size ranging from about 6 to about40 microns and a density of about 1-1.3 g/cm³. The EXPANCEL® DEmicrospheres have an average particle size ranging from about 20 toabout 150 microns and a density of about 0.03-0.07 g/cm³.

Suitable solvents for making a composite particulate in the form ofcollapsed microspheres having colorants dispersed therein are those asset forth with respect to the fused agglomerated composite particulateas described above, and in the same general amounts.

Upon mixing with untreated hollow microspheres, the polar organicsolvent can swell the polymeric shells of the hollow microspheressignificantly and thereby convert the gas-tight polymeric shells of theuntreated hollow microspheres into a gelled state with multiplemicro-channels or pores formed therein.

The colorants used in formation of the collapsed microsphere are thesame as those set forth with respect to the fused agglomerate and in thesame general amounts.

It is possible to incorporate two or more different types of colorantsinto the microsphere to create unique visual effects. In one specificembodiment of the composite particulate, two or more different types ofpigment particles are incorporated into the microspheres.

It is preferred that where the composite particulate is in the form ofcollapsed microspheres, that the average particle size of the colorantsused should be significantly smaller than that of the hollowmicrospheres so that the colorants can readily enter and be entrapped bythe hollow microspheres that forms the clear thermoplastic material.Preferably, the average size of the colorant particles is less thanabout 1 micron, more preferably from about 0.001 micron to about 0.1micron, and most preferably from about 0.01 to about 0.05 micron.

The hollow microspheres, the solvent and the colorant as describedherein are mixed together, either simultaneously or sequentially, toform a gelled mixture. If mixed sequentially, the ingredients can beadded and mixed in any suitable order. For example, the hollowmicrospheres and the colorant can be blended together first, followed byaddition of the solvent to form a slurry. For another example, thecolorant can be dispensed in the solvent first, and then mixed with thehollow microspheres. For still another example, the hollow microspherescan be added to the organic solvent to form a gel first, and thecolorants are then added into the gel. In any event, all the ingredientsare well mixed until a homogenous mixture is formed. The weight ratiobetween the hollow microspheres and the polar organic solvent ispreferably from about 1:3 to about 1:100 and more preferably from about1:20 to about 1:50, so that the polymeric shells of the hollowmicrospheres can be sufficiently swelled by the solvent. The weightratio between the colorants and the hollow microspheres can range widelyfrom about 1:10 to about 100:1, preferably from about 2:3 to about 10:1,and more preferably from about 1:1 to about 2:1.

Because the polymeric shells of hollow microspheres are comprised of anon-crosslinked or weakly crosslinked polymer the solvent molecules,which are sufficiently small in comparison with the polymeric molecules,can enter between the polymeric chains, interrupt the intermolecularbonds between neighboring polymeric chains, and pull the polymericchains apart from each other. Consequently, the polymeric shells of thehollow microspheres are swelled by the polar organic solvent, so as toform a gelled mixture that contains porous networks of interconnectedpolymeric chains spanning or dispersed throughout the volume of thesolvent. The polymeric shells of the microspheres in such a gelled stateare no longer gas-tight, but have become porous, i.e., with sufficientlylarge micro-channels therein to allow entry of the colorant into thesufficiently swelled microspheres. At the same time, the expandablefluid exit from such microspheres through the micro-channels, causingthe gelled polymeric shells to collapse or implode and resulting inshrunken microspheres with significantly decreased overall volume. Inthis manner, the colorants become entrapped within the collapsedpolymeric shells of the shrunk microspheres.

Such shrunken microspheres may have an average particle size rangingfrom about 1 to 15 microns, and more from about 5 microns to about 8microns. The shrunk microspheres are significantly smaller in size thanthe untreated hollow microspheres. Further, the shrunken microspheresare no longer hollow, but are now filled by the pigment particles withlittle or no empty space left therein. At the same time, the polymericshells of the microspheres remain in a gelled state, i.e., swelled bythe polar organic solvent. It is important to note that the shrunkenmicrospheres of the present invention, although morphologically andvolumetrically modified by the gelling process, remain as separateparticles in the gelled mixture with little or no coalescence.Subsequent drying of the gelled mixture therefore forms finefree-flowing powders, which contain microspheres with well-definedsurface boundaries and minimum clumping or agglomeration.

The gelling process as described herein is fundamentally different fromthe well known sol gel process. In a typical sol-gel process, metalalkoxide and metal chloride precursors are first solubilized to form asolution (sol) and then undergo hydrolysis and polycondensationreactions to form a colloid system composed of solid particles dispersedin a solvent, followed by evolvement toward the formation of aninorganic network containing a liquid phase (gel), which can be dried toremove the liquid phase from the gel thus forming a porous material. Incontrast, the gelling process of the present invention does not involvehydrolysis or polycondensation reactions, and it forms a network ofwater-insoluble polymeric chains dispersed in the polar organic solvent.

The gelled mixture as described hereinabove can be subjected tode-gassing, in which the gelled mixture is placed under a reducedpressure or vacuum conditions, so as to remove the expandable fluid fromthe gelled mixture. Subsequently, a second solvent that is miscible withthe polar organic solvent previously used for swelling/gelling themicrospheres can be added into the de-gassed gelled mixture withsufficient agitation, so as to “quench” the gelled mixture by separatingthe swelled microspheres from one another. For example, when the polarorganic solvent is acetone, the second solvent can be water, which ismiscible with acetone. Due to the immiscibility between the polarorganic solvent and the second solvent, the microspheres become morespatially separated from one another and therefore more dispersed. Suchfurther dispersion of the microspheres functions to minimize the risk ofcoalescence during subsequent drying of the gelled mixture. Furtherseparation of the microspheres can be achieved by a filtration orcentrifugation step, which is optional for the purpose of the presentinvention.

After the de-gassing and quenching steps, both the polar organic solventand the second solvent are preferably removed from the gelled mixture toform dry, free-flowing powders containing the microspheres with thesolid particles entrapped therein. Removal of the polar organic solventand the second solvent can be readily achieved by various separationand/or drying techniques well known in the art, such as decantation,centrifugation, filtration, solvent extraction, air drying, vacuumdrying, freeze drying, spray drying, fluid bed drying, supercriticalfluid drying, and the like. The polymeric shells, which have beenpreviously swelled by the polar organic solvent and become porous withmicro-channels extending there through, shrink significantly and losetheir porosity after being dried. In other words, the micro-channelsformed through the swelled polymeric shells of the microspheres duringthe gelling step close up after the drying step, thereby securelyentrapping the pigment particles inside the microspheres. To minimizeagglomeration between the dried microspheres, the resulting powders canbe further subject to milling and sieving through one or more screens.

In order to eliminate or minimize the potential risk of the entrappedpigment particles leaking out of the dried microspheres, the resultingcomposite particulate can be coated or otherwise surface-treated.Suitable coating ingredients include those set forth herein, such assilicones, waxes, oils, and the like as described with respect toingredients suitable for use in the compositions of the invention. Wherethe composite particulate is in the form of a collapsed microsphere, itis preferred that the coating be impermeable to liquid to prevent anyliquid from entering into the microsphere and causing the colorantspresent to leak out.

The resulting composite particulates may have an average particle sizeranging from about 1 to about 50 microns, more preferably from about 1to about 15 microns, and most preferably from about 5 to about 8microns, as determined by a Malvern Particle Size Analyzer, availablefrom Malvern Instrument at Worcestershire, UK. The entrapped colorantsmay comprise from about 10% to about 90% of the total weight of thetotal composite particulate, 30% to about 75% of the total weight, andmost preferably from about 40% to about 60% of the total weight.

FIG. 2 depicts the schematic views of an untreated hollow microsphere 10and a microsphere 20 according to one embodiment of the presentinvention, which is formed by processing the untreated hollowmicrosphere 10 according to the method described hereinabove.Specifically, the untreated hollow microsphere 10 includes a gas-tightand deformable polymeric shell 12 with an expandable fluid 14 entrappedtherein. The diameter of the untreated hollow microsphere 10 isapproximately 20 microns. In contrast, the microsphere 20 of the presentinvention includes a collapsed polymeric shell 22 with pigment particles24 entrapped therein and a liquid-impermeable membrane 24 coated over.The diameter of the microsphere 20 is significantly smaller than that ofthe untreated hollow microsphere 10 and approximately ranges from about5 to about 8 microns.

Also suitable are composite particulates in the form of encapsulatedcolorants such as those that are disclosed in U.S. Pat. Nos. 5,223,250;5,531,985; 5,587,148; and 5,733,531, all of which are herebyincorporated by reference in their entirety.

III. The Cosmetic Compositions

The composite particulates may be used to prepare a variety ofcompositions suitable for application to keratinous surfaces, includingbut not limited to creams, lotions, sunscreens, foundation makeup,concealer, eyeshadow, blush, eyeliner, mascara, lipstick, lip gloss,nail enamel, hair products such as shampoo, conditioner, stylingproducts; and so on. The compositions may be in the form of aqueous gelsor dispersions, emulsions, or anhydrous compositions, and in the liquid,semi-solid or solid form. Suitable aqueous gels contain from about 0.1to 99% water from about 1-99.9% of other cosmetic ingredients. Emulsionsmay be in the oil in water or water in oil form, and generally comprisefrom about 0.1 to 99% water and from about 0.1 to 99% oil. Anhydrouscompositions generally contain less than about 1% water, in addition to0.1 to 90% oils, and optionally other ingredients. Such compositions maycontain one or more of the following ingredients.

In general, compositions where the total colorant component comprisesfrom about 30-70 parts, preferably 40-60, most preferably about 50 partsof iron oxide to about 70-30, preferably 60-40, most preferably about 50parts of thermoplastic material provide a desirable color effect thatresults in a natural coverage look. Expressed in a different way, theadvantageous color effect can be achieved with a combination of about50-80 parts composite particulate, more particularly about 2/3 compositeparticulate and about 20-50, more specifically about 1/3 parts ironoxide.

A. Oils

Suitable oils include silicones, esters, vegetable oils, synthetic oils,including but not limited to those set forth herein. Suggested amountsare from about 0.1 to 99%, preferably from about 0.5 to 95%, morepreferably from about 1 to 80%. The oils may be volatile or nonvolatile,and are preferably in the form of a pourable liquid at room temperature.The term “volatile” means that the oil has a measurable vapor pressure,or a vapor pressure of at least about 2 mm. of mercury at 20° C. Theterm “nonvolatile” means that the oil has a vapor pressure of less thanabout 2 mm. of mercury at 20° C.

1. Volatile Oils

Suitable volatile oils generally have a viscosity ranging from about 0.5to 5 centistokes 25° C. and include linear or cyclic silicones,paraffinic hydrocarbons, or mixtures thereof.

(a). Volatile Silicones

Cyclic silicones are one type of volatile silicone that may be used inthe composition, including those having the following formula:

where n=3-6, preferably 4, 5, or 6.

Also suitable are linear volatile silicones, for example, those havingthe general formula:(CH₃)₃Si—O—[Si(CH₃)₂—O]_(n)—Si(CH₃)₃

where n=0, 1, 2, 3, 4, or 5, preferably 0, 1, 2, 3, or 4.

Cyclic and linear volatile silicones are available from variouscommercial sources including Dow Corning Corporation and GeneralElectric. The Dow Corning linear volatile silicones are sold under thetradenames Dow Corning 244, 245, 344, and 200 fluids. These fluidsinclude hexamethyldisiloxane (viscosity 0.65 centistokes (abbreviatedcst)), octamethyltrisiloxane (1.0 cst), decamethyltetrasiloxane (1.5cst), dodecamethylpentasiloxane (2 cst) and mixtures thereof, with allviscosity measurements being at 25° C.

Suitable branched volatile silicones include alkyl trimethicones such asmethyl trimethicone, ethyl trimethicone, propyl trimethicone, butyltrimethicone and the like. Methyl trimethicone may be purchased fromShin-Etsu Silicones and has the trade name TMF 1.5, having the viscosityof 1.5 centistokes at 25° C. Such silicones have the general formula:

wherein each R is independently a C₁₋₄ alkyl, preferably methyl.

(b). Volatile Paraffinic Hydrocarbons

Also suitable as the volatile oils are various straight or branchedchain paraffinic hydrocarbons having 5, 6, 7, 8, 9, 10, 11, 12, 13, 14,15, 16, 17, 18, 19, or 20 carbon atoms, more preferably 8 to 16 carbonatoms. Suitable hydrocarbons include pentane, hexane, heptane, decane,dodecane, tetradecane, tridecane, and C₈₋₂₀ isoparaffins as disclosed inU.S. Pat. Nos. 3,439,088 and 3,818,105, both of which are herebyincorporated by reference.

Such paraffinic hydrocarbons are available from EXXON under the ISOPARStrademark, and from the Permethyl Corporation. Suitable C₁₂ isoparaffinsare manufactured by Permethyl Corporation under the tradename Permethyl99A. Various C₁₆ isoparaffins commercially available, such asisohexadecane (having the tradename Permethyl R), are also suitable.

2. Non-Volatile Oils

A variety of nonvolatile oils are also suitable for use in thecompositions of the invention. The nonvolatile oils generally have aviscosity of greater than about 5 to 10 centistokes at 25° C., and mayrange in viscosity up to about 1,000,000 centistokes at 25° C. Examplesof nonvolatile oils include, but are not limited to:

1. Esters

Suitable esters are mono-, di-, and triesters. The composition maycomprise one or more esters selected from the group, or mixturesthereof.

Monoesters are defined as esters formed by the reaction of amonocarboxylic acid having the formula R—COOH, wherein R is a straightor branched chain saturated or unsaturated alkyl having 2 to 45 carbonatoms, or phenyl; and an alcohol having the formula R—OH wherein R is astraight or branched chain saturated or unsaturated alkyl having 2-30carbon atoms, or phenyl. Both the alcohol and the acid may besubstituted with one or more hydroxyl groups. Either one or both of theacid or alcohol may be a “fatty” acid or alcohol, and may have fromabout 6 to 30 carbon atoms, more preferably 12, 14, 16, 18, or 22 carbonatoms in straight or branched chain, saturated or unsaturated form.Examples of monoester oils that may be used in the compositions of theinvention include hexyl laurate, butyl isostearate, hexadecylisostearate, cetyl palmitate, isostearyl neopentanoate, stearylheptanoate, isostearyl isononanoate, steary lactate, stearyl octanoate,stearyl stearate, isononyl isononanoate, and so on.

Suitable diesters are the reaction product of a dicarboxylic acid and analiphatic or aromatic alcohol, or an aliphatic or aromatic alcoholhaving at least two substituted hydroxyl groups and a monocarboxylicacid. The dicarboxylic acid may contain from 2 to 30 carbon atoms, andmay be in the straight or branched chain, saturated or unsaturated form.The dicarboxylic acid may be substituted with one or more hydroxylgroups. The aliphatic or aromatic alcohol may also contain 2 to 30carbon atoms, and may be in the straight or branched chain, saturated,or unsaturated form. Preferably, one or more of the acid or alcohol is afatty acid or alcohol, i.e. contains 12-22 carbon atoms. Thedicarboxylic acid may also be an alpha hydroxy acid. The ester may alsobe in the dimer or trimer form. Examples of diester oils that may beused in the compositions of the invention include those having a lowerviscosity, e.g. diisotearyl malate, neopentyl glycol dioctanoate,dibutyl sebacate, dicetearyl dimer dilinoleate, dicetyl adipate,diisocetyl adipate, diisononyl adipate, diisostearyl dimer dilinoleate,diisostearyl fumarate, diisostearyl malate, dioctyl malate, and so on.

Suitable triesters comprise the reaction product of a tricarboxylic acidand an aliphatic or aromatic alcohol, or alternatively, the reactionproduct of an aliphatic or aromatic alcohol having three or moresubstituted hydroxyl groups with a monocarboxylic acid. As with themono- and diesters mentioned above, the acid and alcohol contain 2 to 30carbon atoms, and may be saturated or unsaturated, straight or branchedchain, and may be substituted with one or more hydroxyl groups.Preferably, one or more of the acid or alcohol is a fatty acid oralcohol containing 12 to 22 carbon atoms. Examples of triesters includeesters of arachidonic, citric, or behenic acids, such as triarachidin,tributyl citrate, triisostearyl citrate, tri C₁₂₋₁₃ alkyl citrate,tricaprylin, tricaprylyl citrate, tridecyl behenate, trioctyldodecylcitrate, tridecyl behenate; or tridecyl cocoate, tridecyl isononanoate,and so on.

Esters suitable for use in the composition are further described in theC.T.F.A. Cosmetic Ingredient Dictionary and Handbook, Eleventh Edition,2006, under the classification of “Esters”, the text of which is herebyincorporated by reference in its entirety.

2. Hydrocarbon Oils

It may be desirable to incorporate one or more nonvolatile hydrocarbonoils into the composition. Suitable nonvolatile hydrocarbon oils includeparaffinic hydrocarbons and olefins, preferably those having greaterthan about 20 carbon atoms. Examples of such hydrocarbon oils includeC₂₄₋₂₈ olefins, C₃₀₋₄₅ olefins, C₂₀₋₄₀ isoparaffins, hydrogenatedpolyisobutene, polyisobutene, polydecene, hydrogenated polydecene,mineral oil, pentahydrosqualene, squalene, squalane, and mixturesthereof. In one preferred embodiment such hydrocarbons have a molecularweight ranging from about 300 to 1000 Daltons.

3. Glyceryl Esters of Fatty Acids

Synthetic or naturally occurring glyceryl esters of fatty acids, ortriglycerides, are also suitable for use in the compositions. Bothvegetable and animal sources may be used. Examples of such oils includecastor oil, lanolin oil, C₁₀₋₁₈ triglycerides,caprylic/capric/triglycerides, sweet almond oil, apricot kernel oil,sesame oil, camelina sativa oil, tamanu seed oil, coconut oil, corn oil,cottonseed oil, linseed oil, ink oil, olive oil, palm oil, illipebutter, rapeseed oil, soybean oil, grapeseed oil, sunflower seed oil,walnut oil, and the like.

Also suitable are synthetic or semi-synthetic glyceryl esters, such asfatty acid mono-, di-, and triglycerides which are natural fats or oilsthat have been modified, for example, mono-, di- or triesters of polyolssuch as glycerin. In an example, a fatty (C₁₂₋₂₂) carboxylic acid isreacted with one or more repeating glyceryl groups. glyceryl stearate,diglyceryl diiosostearate, polyglyceryl-3 isostearate, polyglyceryl-4isostearate, polyglyceryl-6 ricinoleate, glyceryl dioleate, glyceryldiisotearate, glyceryl tetraisostearate, glyceryl trioctanoate,diglyceryl distearate, glyceryl linoleate, glyceryl myristate, glycerylisostearate, PEG castor oils, PEG glyceryl oleates, PEG glycerylstearates, PEG glyceryl tallowates, and so on.

4. Nonvolatile Silicones

Nonvolatile silicone oils, both water soluble and water insoluble, arealso suitable for use in the composition. Such silicones preferably havea viscosity ranging from about greater than 5 to 800,000 cst, preferably20 to 200,000 cst at 25° C. Suitable water insoluble silicones includeamine functional silicones such as amodimethicone.

For example, such nonvolatile silicones may have the following generalformula:

wherein R and R′ are each independently C₁₋₃₀ straight or branchedchain, saturated or unsaturated alkyl, phenyl or aryl, trialkylsiloxy,and x and y are each independently 1-1,000,000; with the proviso thatthere is at least one of either x or y, and A is alkyl siloxy endcapunit.

Preferred is where A is a methyl siloxy endcap unit; in particulartrimethylsiloxy, and R and R′ are each independently a C₁₋₃₀ straight orbranched chain alkyl, phenyl, or trimethylsiloxy, more preferably aC₁₋₂₂ alkyl, phenyl, or trimethylsiloxy, most preferably methyl, phenyl,or trimethylsiloxy, and resulting silicone is dimethicone, phenyldimethicone, diphenyl dimethicone, phenyl trimethicone, ortrimethylsiloxyphenyl dimethicone. Other examples include alkyldimethicones such as cetyl dimethicone, and the like wherein at leastone R is a fatty alkyl (C₁₂, C₁₄, C₁₆, C₁₈, C₂₀, or C₂₂), and the otherR is methyl, and A is a trimethylsiloxy endcap unit, provided such alkyldimethicone is a pourable liquid at room temperature. Phenyltrimethicone can be purchased from Dow Corning Corporation under thetradename 556 Fluid. Trimethylsiloxyphenyl dimethicone can be purchasedfrom Wacker-Chemie under the tradename PDM-1000. Cetyl dimethicone, alsoreferred to as a liquid silicone wax, may be purchased from Dow Corningas Fluid 2502, or from DeGussa Care & Surface Specialties under thetrade names Abil Wax 9801, or 9814.

B. Humectants

The compositions of the invention may also contain one or morehumectants. If present, suggested ranges are from about 0.001 to 50%,preferably from about 0.01 to 45%, more preferably from about 0.05 to40% by weight of the total composition. Examples of suitable humectantsinclude glycols, sugars, and the like. Suitable glycols are in monomericor polymeric form and include polyethylene and polypropylene glycolssuch as PEG 4-200, which are polyethylene glycols having from 4 to 200repeating ethylene oxide units; as well as C₁₋₆ alkylene glycols such aspropylene glycol, butylene glycol, pentylene glycol, and the like.Suitable sugars, some of which are also polyhydric alcohols, are alsosuitable humectants. Examples of such sugars include glucose, fructose,honey, hydrogenated honey, inositol, maltose, mannitol, maltitol,sorbitol, sucrose, xylitol, xylose, trehalose, and so on. Also suitableis urea or sugar derivatives, e.g. ethylhexylglycerin. In one preferredembodiment, the humectants used in the composition of the invention areC₁₋₆, preferably C₂₄ alkylene glycols, most particularly butyleneglycol.

C. Surfactants

If desired, the compositions of the invention may contain one or moresurfactants. This is particularly desirable when the composition is inthe form of an aqueous gel or emulsion. If present, the surfactant mayrange from about 0.001 to 50%, preferably from about 0.005 to 40%, morepreferably from about 0.01 to 35% by weight of the total composition.Suitable surfactants may be silicone or organic, nonionic, anionic,amphoteric or zwitterionic. Such surfactants include, but are notlimited to, those set forth herein.

1. Silicone Surfactants

Suitable silicone surfactants include polyorganosiloxane polymers thathave amphiphilic properties, for example contain hydrophilic radicalsand lipophilic radicals. These silicone surfactants may be liquids orsolids at room temperature.

(a). Dimethicone Copolyols or Alkyl Dimethicone Copolyols

One type of silicone surfactant that may be used is generically referredto as dimethicone copolyol or alkyl dimethicone copolyol. It may beeither a water-in-oil or oil-in-water surfactant having anHydrophile/Lipophile Balance (HLB) ranging from about 2 to 18.Preferably the silicone surfactant is a nonionic surfactant having anHLB ranging from about 2 to 12, preferably about 2 to 10, mostpreferably about 4 to 6. The term “hydrophilic radical” means a radicalthat, when substituted onto the organosiloxane polymer backbone, confershydrophilic properties to the substituted portion of the polymer.Examples of radicals that will confer hydrophilicity arehydroxy-polyethyleneoxy, hydroxyl, carboxylates, and mixtures thereof.The term “lipophilic radical” means an organic radical that, whensubstituted onto the organosiloxane polymer backbone, confers lipophilicproperties to the substituted portion of the polymer. Examples oforganic radicals that will confer lipophilicity are C₁₋₄₀ straight orbranched chain alkyl, fluoro, aryl, aryloxy, C₁₋₄₀ hydrocarbyl acyl,hydroxy-polypropyleneoxy, or mixtures thereof.

One type of suitable silicone surfactant has the general formula:

wherein p is 0-40 (the range including all numbers between and subrangessuch as 2, 3, 4, 13, 14, 15, 16, 17, 18, etc.), and PE is(—C₂H₄O)_(a)—(-C₃H₆O)_(b)—H wherein a is 0 to 25, b is 0-25 with theproviso that both a and b cannot be 0 simultaneously, x and y are eachindependently ranging from 0 to 1 million with the proviso that theyboth cannot be 0 simultaneously. In one preferred embodiment, x, y, z,a, and b are such that the molecular weight of the polymer ranges fromabout 5,000 to about 500,000, more preferably from about 10,000 to100,000, and is most preferably approximately about 50,000 and thepolymer is generically referred to as dimethicone copolyol.

One type of silicone surfactant is wherein p is such that the long chainalkyl is cetyl or lauryl, and the surfactant is called, generically,cetyl dimethicone copolyol or lauryl dimethicone copolyol respectively.

In some cases the number of repeating ethylene oxide or propylene oxideunits in the polymer are also specified, such as a dimethicone copolyolthat is also referred to as PEG-15/PPG-10 dimethicone, which refers to adimethicone having substituents containing 15 ethylene glycol units and10 propylene glycol units on the siloxane backbone. It is also possiblefor one or more of the methyl groups in the above general structure tobe substituted with a longer chain alkyl (e.g. ethyl, propyl, butyl,etc.) or an ether such as methyl ether, ethyl ether, propyl ether, butylether, and the like.

Examples of silicone surfactants are those sold by Dow Corning under thetradename 5225C Formulation Aid, having the CTFA name cyclopentasiloxane(and) PEG/PPG-18/18 dimethicone; or Dow Corning 190 Surfactant havingthe CTFA name PEG/PPG-18/18 dimethicone; or Dow Corning 193 Fluid, DowCorning 5200 having the CTFA name lauryl PEG/PPG-18/18 methicone; orAbil EM 90 having the CTFA name cetyl PEG/PPG-14/14 dimethicone sold byGoldschmidt; or Abil EM 97 having the CTFA name bis-cetyl PEG/PPG-14/14dimethicone sold by Goldschmidt; or Abil WE 09 having the CTFA namecetyl PEG/PPG-10/1 dimethicone in a mixture also containingpolyglyceryl-4 isostearate and hexyl laurate; or KF-6011 sold byShin-Etsu Silicones having the CTFA name PEG-11 methyl etherdimethicone; KF-6012 sold by Shin-Etsu Silicones having the CTFA namePEG/PPG-20/22 butyl ether dimethicone; or KF-6013 sold by Shin-EtsuSilicones having the CTFA name PEG-9 dimethicone; or KF-6015 sold byShin-Etsu Silicones having the CTFA name PEG-3 dimethicone; or KF-6016sold by Shin-Etsu Silicones having the CTFA name PEG-9 methyl etherdimethicone; or KF-6017 sold by Shin-Etsu Silicones having the CTFA namePEG-10 dimethicone; or KF-6038 sold by Shin-Etsu Silicones having theCTFA name lauryl PEG-9 polydimethylsiloxyethyl dimethicone.

(b). Crosslinked Silicone Surfactants

Crosslinked silicone surfactants, often referred to as emulsifyingelastomers are suitable. Typically these polyoxyalkylenated siliconeelastomers are crosslinked organopolysiloxanes that may be obtained by acrosslinking addition reaction of diorganopolysiloxane comprising atleast one hydrogen bonded to silicon and of a polyoxyalkylene comprisingat least two ethylenically unsaturated groups. In at least oneembodiment, the polyoxyalkylenated crosslinked organo-polysiloxanes areobtained by a crosslinking addition reaction of a diorganopolysiloxanecomprising at least two hydrogens each bonded to a silicon, and apolyoxyalkylene comprising at least two ethylenically unsaturatedgroups, optionally in the presence of a platinum catalyst, as described,for example, in U.S. Pat. No. 5,236,986 and U.S. Pat. No. 5,412,004,U.S. Pat. No. 5,837,793 and U.S. Pat. No. 5,811,487, the contents ofwhich are incorporated by reference.

Polyoxyalkylenated silicone elastomers that may be used include thosesold by Shin-Etsu Silicones under the names KSG-21, KSG-20, KSG-30,KSG-31, KSG-32, KSG-33; KSG-210 which is dimethicone/PEG-10/15crosspolymer dispersed in dimethicone; KSG-310 which is PEG-15 lauryldimethicone crosspolymer; KSG-320 which is PEG-15 lauryl dimethiconecrosspolymer dispersed in isododecane; KSG-330 (the former dispersed intriethylhexanoin), KSG-340 which is a mixture of PEG-10 lauryldimethicone crosspolymer and PEG-15 lauryl dimethicone crosspolymer.

Also suitable are polyglycerolated silicone elastomers like thosedisclosed in PCT/WO 2004/024798, which is hereby incorporated byreference in its entirety. Such elastomers include Shin-Etsu's KSGseries, such as KSG-710 which is dimethicone/polyglycerin-3 crosspolymerdispersed in dimethicone; or lauryl dimethicone/polyglycerin-3crosspolymer dispersed in a variety of solvent such as isododecane,dimethicone, triethylhexanoin, sold under the Shin-Etsu tradenamesKSG-810, KSG-820, KSG-830, or KSG-840. Also suitable are silicones soldby Dow Corning under the tradenames 9010 and DC9011.

One preferred crosslinked silicone elastomer emulsifier isdimethicone/PEG-10/15 crosspolymer, which provides excellent aestheticsdue to its elastomeric backbone, but also surfactancy properties.

2. Organic Nonionic Surfactants

The composition may comprise one or more nonionic organic surfactants.Suitable nonionic surfactants include alkoxylated alcohols, or ethers,formed by the reaction of an alcohol with an alkylene oxide, usuallyethylene or propylene oxide. Preferably the alcohol is either a fattyalcohol having 6 to 30 carbon atoms. Examples of such ingredientsinclude Steareth 2-100, which is formed by the reaction of stearylalcohol and ethylene oxide and the number of ethylene oxide units rangesfrom 2 to 100; Beheneth 5-30 which is formed by the reaction of behenylalcohol and ethylene oxide where the number of repeating ethylene oxideunits is 5 to 30; Ceteareth 2-100, formed by the reaction of a mixtureof cetyl and stearyl alcohol with ethylene oxide, where the number ofrepeating ethylene oxide units in the molecule is 2 to 100; Ceteth 1-45which is formed by the reaction of cetyl alcohol and ethylene oxide, andthe number of repeating ethylene oxide units is 1 to 45, Laureth 2-100,formed by the reaction of lauryl alcohol and ethylene oxide where thenumber of repeating ethylene oxide units is 2 to 100, and so on.

Other alkoxylated alcohols are formed by the reaction of fatty acids andmono-, di- or polyhydric alcohols with an alkylene oxide. For example,the reaction products of C₆₋₃₀ fatty carboxylic acids and polyhydricalcohols which are monosaccharides such as glucose, galactose, methylglucose, and the like, with an alkoxylated alcohol. Examples includepolymeric alkylene glycols reacted with glyceryl fatty acid esters suchas PEG glyceryl oleates, PEG glyceryl stearate; or PEGpolyhydroxyalkanotes such as PEG dipolyhydroxystearate wherein thenumber of repeating ethylene glycol units ranges from 3 to 1000. Alsosuitable are ethoxylated propoxylated derivatives of C6-30 saturated orunsaturated fatty acids, for example, Di-PPG-2 myreth-10 adipate,Di-PPG-2 Ceteth-4 adipate, Di-PPG Myristyl Ether Adipate.

Other nonionic surfactants that may be used are formed by the reactionof a carboxylic acid with an alkylene oxide or with a polymeric ether ormonomeric, homopolymeric, or block copolymeric ethers; or alkoxylatedsorbitan and alkoxylated sorbitan derivatives. For example,alkoxylation, in particular ethoxylation of sorbitan providespolyalkoxylated sorbitan derivatives. Esterification of polyalkoxylatedsorbitan provides sorbitan esters such as the polysorbates. For example,the polyalkyoxylated sorbitan can be esterified with C6-30, preferablyC12-22 fatty acids. Examples of such ingredients include Polysorbates20-85, sorbitan oleate, sorbitan sesquioleate, sorbitan palmitate,sorbitan sesquiisostearate, sorbitan stearate, and so on.

D. Structuring Agents

It may also be desirable to include one or more structuring agents inthe composition. Structuring agents will increase the viscosity, hencestructure, the composition. Structuring agents may be lipophilic orhydrophilic, and form part of the aqueous or non-aqueous phase of thecomposition. If present, the structuring agent may range from about 0.1to 60%, preferably from about 0.5 to 50%, more preferably from about 1to 45% of the composition.

Desirable structuring agents include silicone elastomers, silicone gumsor waxes, natural or synthetic waxes, polyamides, silicone polyamidesand the like.

1. Silicone Elastomers

Silicone elastomers include those that are formed by additionreaction-curing, by reacting an SiH-containing diorganosiloxane and anorganopolysiloxane having terminal olefinic unsaturation, or analpha-omega diene hydrocarbon, in the presence of a platinum metalcatalyst. Such elastomers may also be formed by other reaction methodssuch as condensation-curing organopolysiloxane compositions in thepresence of an organotin compound via a dehydrogenation reaction betweenhydroxyl-terminated diorganopolysiloxane and SiH-containingdiorganopolysiloxane or alpha omega diene; or by condensation-curingorganopolysiloxane compositions in the presence of an organotin compoundor a titanate ester using a condensation reaction between anhydroxyl-terminated diorganopolysiloxane and a hydrolysableorganosiloxane; peroxide-curing organopolysiloxane compositions whichthermally cure in the presence of an organoperoxide catalyst.

One type of elastomer that may be suitable is prepared by additionreaction-curing an organopolysiloxane having at least 2 lower alkenylgroups in each molecule or an alpha-omega diene; and anorganopolysiloxane having at least 2 silicon-bonded hydrogen atoms ineach molecule; and a platinum-type catalyst. While the lower alkenylgroups such as vinyl, can be present at any position in the molecule,terminal olefinic unsaturation on one or both molecular terminals ispreferred. The molecular structure of this component may be straightchain, branched straight chain, cyclic, or a network. Theseorganopolysiloxanes are exemplified by methylvinylsiloxanes,methylvinylsiloxane-dimethylsiloxane copolymers,dimethylvinylsiloxy-terminated dimethylpolysiloxanes,dimethylvinylsiloxy-terminated dimethylsiloxane-methylphenylsiloxanecopolymers, dimethylvinylsiloxy-terminateddimethylsiloxane-diphenylsiloxane-methylvinylsiloxane copolymers,trimethylsiloxy-terminated dimethylsiloxane-methylvinylsiloxanecopolymers, trimethylsiloxy-terminateddimethylsiloxane-methylphenylsiloxane-methylvinylsiloxane copolymers,dimethylvinylsiloxy-terminatedmethyl(3,3,3-trifluoropropyl)polysiloxanes, anddimethylvinylsiloxy-terminateddimethylsiloxane-methyl(3,3,-trifluoropropyl)siloxane copolymers,decadiene, octadiene, heptadiene, hexadiene, pentadiene, or tetradiene,or tridiene.

Curing proceeds by the addition reaction of the silicon-bonded hydrogenatoms in the dimethyl methylhydrogen siloxane, with the siloxane oralpha-omega diene under catalysis using the catalyst mentioned herein.To form a highly crosslinked structure, the methyl hydrogen siloxanemust contain at least 2 silicon-bonded hydrogen atoms in each moleculein order to optimize function as a crosslinker.

The catalyst used in the addition reaction of silicon-bonded hydrogenatoms and alkenyl groups, and is concretely exemplified bychloroplatinic acid, possibly dissolved in an alcohol or ketone and thissolution optionally aged, chloroplatinic acid-olefin complexes,chloroplatinic acid-alkenylsiloxane complexes, chloroplatinicacid-diketone complexes, platinum black, and carrier-supported platinum.

Examples of suitable silicone elastomers for use in the compositions ofthe invention may be in the powder form, or dispersed or solubilized insolvents such as volatile or nonvolatile silicones, or siliconecompatible vehicles such as paraffinic hydrocarbons or esters. Examplesof silicone elastomer powders include vinyl dimethicone/methiconesilesquioxane crosspolymers like Shin-Etsu's KSP-100, KSP-101, KSP-102,KSP-103, KSP-104, KSP-105, hybrid silicone powders that contain afluoroalkyl group like Shin-Etsu's KSP-200 which is a fluoro-siliconeelastomer, and hybrid silicone powders that contain a phenyl group suchas Shin-Etsu's KSP-300, which is a phenyl substituted siliconeelastomer; and Dow Corning's DC 9506. Examples of silicone elastomerpowders dispersed in a silicone compatible vehicle includedimethicone/vinyl dimethicone crosspolymers supplied by a variety ofsuppliers including Dow Corning Corporation under the tradenames 9040 or9041, GE Silicones under the tradename SFE 839, or Shin-Etsu Siliconesunder the tradenames KSG-15, 16, 18. KSG-15 has the CTFA namecyclopentasiloxane/dimethicone/vinyl dimethicone crosspolymer. KSG-18has the INCI name phenyl trimethicone/dimethicone/phenyl vinyldimethicone crosspolymer. Silicone elastomers may also be purchased fromGrant Industries under the Gransil trademark. Also suitable are siliconeelastomers having long chain alkyl substitutions such as lauryldimethicone/vinyl dimethicone crosspolymers supplied by Shin Etsu underthe tradenames KSG-31, KSG-32, KSG-41, KSG-42, KSG-43, and KSG-44.Cross-linked organopolysiloxane elastomers useful in the presentinvention and processes for making them are further described in U.S.Pat. No. 4,970,252 to Sakuta et al., issued Nov. 13, 1990; U.S. Pat. No.5,760,116 to Kilgour et al., issued Jun. 2, 1998; U.S. Pat. No.5,654,362 to Schulz, Jr. et al. issued Aug. 5, 1997; and Japanese PatentApplication JP 61-18708, assigned to Pola Kasei Kogyo K K, each of whichare herein incorporated by reference in its entirety.

2. Silicone Gums

Silicone gums are also suitable structuring agents. The term “gum” meansa silicone polymer having a degree of polymerization sufficient toprovide a silicone having a gum-like texture. In certain cases thesilicone polymer forming the gum may be crosslinked. The silicone gumtypically has a viscosity ranging from about 500,000 to 100 million cstat 25° C., preferably from about 600,000 to 20 million, more preferablyfrom about 600,000 to 12 million cst. All ranges mentioned hereininclude all subranges, e.g. 550,000; 925,000; 3.5 million.

Such silicone gums may be purchased in pure form from a variety ofsilicone manufacturers including Wacker-Chemie or Dow Corning, and thelike. Such silicone gums include those sold by Wacker-Belsil under thetrade names CM3092, Wacker-Belsil 1000, or Wacker-Belsil DM 3096. Asilicone gum where X is OH, also referred to as dimethiconol, isavailable from Dow Corning Corporation under the trade name 1401. Thesilicone gum may also be purchased in the form of a solution ordispersion in a silicone compatible vehicle such as volatile ornonvolatile silicone. An example of such a mixture may be purchased fromBarnet Silicones under the HL-88 tradename, having the INCI namedimethicone.

3. Polyamides or Silicone Polyamides

Also suitable as oil phase structuring agents are various types ofpolymeric compounds such as polyamides or silicone polyamides.

The term silicone polyamide means a polymer comprised of siliconemonomers and monomers containing amide groups as further describedherein. The silicone polyamide preferably comprises moieties of thegeneral formula:

where X is a linear or branched alkylene having from about 1-30 carbonatoms; R₁, R₂, R₃, and R₄ are each independently C₁₋₃₀ straight orbranched chain alkyl which may be substituted with one or more hydroxylor halogen groups; phenyl which may be substituted with one or moreC₁₋₃₀ alkyl groups, halogen, hydroxyl, or alkoxy groups; or a siloxanechain having the general formula:

and Y is:

(a) a linear or branched alkylene having from about 1-40 carbon atomswhich may be substituted with (i) one or more amide groups having thegeneral formula R₁CONR₁, or (ii) C₅₋₆ cyclic ring, or (iii) phenylenewhich may be substituted with one or more C₁₋₁₀ alkyl groups, or (iv)hydroxy, or (v) C₃₋₈ cycloalkane, or (vi) C₁₋₂₀ alkyl which may besubstituted with one or more hydroxy groups, or (vii) C₁₋₁₀ alkylamines; or

(b) TR₅R₆R₇

wherein R₅, R₆, and R₇, are each independently a C₁₋₁₀ linear orbranched alkylenes, and T is CR₈ wherein R₈ is hydrogen, a trivalentatom N, P, or Al, or a C₁₋₃₀ straight or branched chain alkyl which maybe substituted with one or more hydroxyl or halogen groups; phenyl whichmay be substituted with one or more C₁₋₃₀ alkyl groups, halogen,hydroxyl, or alkoxy groups; or a siloxane chain having the generalformula:

Preferred is where R₁, R₂, R₃, and R₄ are C₁₋₁₀, preferably methyl; andX and Y is a linear or branched alkylene. Preferred are siliconepolyamides having the general formula:

wherein a and b are each independently sufficient to provide a siliconepolyamide polymer having a melting point ranging from about 60 to 120°C., and a molecular weight ranging from about 40,000 to 500,000 Daltons.One type of silicone polyamide that may be used in the compositions ofthe invention may be purchased from Dow Corning Corporation under thetradename Dow Corning 2-8178 gellant which has the CTFA namenylon-611/dimethicone copolymer which is sold in a compositioncontaining PPG-3 myristyl ether.

Also suitable are polyamides such as those purchased from ArizonaChemical under the tradenames Uniclear and Sylvaclear. Such polyamidesmay be ester terminated or amide terminated. Examples of esterterminated polyamides include, but are not limited to those having thegeneral formula:

wherein n denotes a number of amide units such that the number of estergroups ranges from about 10% to 50% of the total number of ester andamide groups; each R₁ is independently an alkyl or alkenyl groupcontaining at least 4 carbon atoms; each R₂ is independently a C₄₋₄₂hydrocarbon group, with the proviso that at least 50% of the R₂ groupsare a C30-42 hydrocarbon; each R₃ is independently an organic groupcontaining at least 2 carbon atoms, hydrogen atoms and optionally one ormore oxygen or nitrogen atoms; and each R₄ is independently a hydrogenatom, a C₁₋₁₀ alkyl group or a direct bond to R₃ or to another R₄, suchthat the nitrogen atom to which R₃ and R₄ are both attached forms partof a heterocyclic structure defined by R₄—N—R₃, with at least 50% of thegroups R₄ representing a hydrogen atom.

Ester and amide terminated polyamides that may be used include thosesold by Arizona Chemical under the tradenames Sylvaclear A200V orA2614V, both having the CTFA name ethylenediamine/hydrogenated dimerdilinoleate copolymer/bis-di-C₁₄₋₁₈ alkyl amide; Sylvaclear AF1900V;Sylvaclear C75V having the CTFA name bis-stearylethylenediamine/neopentyl glycol/stearyl hydrogenated dimer dilinoleatecopolymer; Sylvaclear PA1200V having the CTFA name Polyamide-3;Sylvaclear PE400V; Sylvaclear WF1500V; or Uniclear, such as Uniclear100VG having the INCI name ethylenediamine/stearyl dimer dilinoleatecopolymer; or ethylenediamine/stearyl dimer ditallate copolymer. Otherexamples of suitable polyamides include those sold by Henkel under theVersamid trademark (such as Versamid 930, 744, 1655), or by OlinMathieson Chemical Corp. under the brand name Onamid S or Onamid C.

4. Natural or Synthetic Organic Waxes

Also suitable as structuring agents may be one or more natural orsynthetic waxes such as animal, vegetable, or mineral waxes. Preferablysuch waxes will have a higher melting point such as from about 60 to150° C., more preferably from about 65 to 100° C. Examples of such waxesinclude waxes made by Fischer-Tropsch synthesis, such as polyethylene orsynthetic wax; or various vegetable waxes such as bayberry, candelilla,ozokerite, acacia, beeswax, ceresin, cetyl esters, flower wax, citruswax, carnauba wax, jojoba wax, japan wax, polyethylene,microcrystalline, rice bran, lanolin wax, mink, montan, bayberry,ouricury, ozokerite, palm kernel wax, paraffin, avocado wax, apple wax,shellac wax, clary wax, spent grain wax, grape wax, and polyalkyleneglycol derivatives thereof such as PEG6-20 beeswax, or PEG-12 carnaubawax; or fatty acids or fatty alcohols, including esters thereof, such ashydroxystearic acids (for example 12-hydroxy stearic acid), tristearin,tribehenin, oleic acid, stearic acid, and so on.

5. Montmorillonite Minerals

One type of structuring agent that may be used comprises natural orsynthetic montmorillonite minerals such as hectorite, bentonite, andquaternized derivatives thereof, which are obtained by reacting theminerals with a quaternary ammonium compound, such as stearalkoniumbentonite, hectorites, quaternized hectorites such as Quaternium-18hectorite, attapulgite, carbonates such as propylene carbonate,bentones, and the like.

6. Silicas and Silicates

Another type of structuring agent that may be used is silica, silicates,or silica silylate, and alkali metal or alkaline earth metal derivativesthereof. These silicas and silicates are generally found in theparticulate form and include silica, silica silylate, magnesium aluminumsilicate, and the like.

Also suitable as structuring agents are various types ofpolysaccharides, for example xanthan gum.

E. Sunscreens

It may also be desirable to include one or more sunscreens in thecompositions of the invention. Such sunscreens include chemical UVA orUVB sunscreens or physical sunscreens in the particulate form.

1. UVA Chemical Sunscreens

If desired, the composition may comprise one or more UVA sunscreens. Theterm “UVA sunscreen” means a chemical compound that blocks UV radiationin the wavelength range of about 320 to 400 nm. Preferred UVA sunscreensare dibenzoylmethane compounds having the general formula

wherein R₁ is H, OR and NRR wherein each R is independently H, C₁₋₂₀straight or branched chain alkyl; R₂ is H or OH; and R₃ is H, C₁₋₂₀straight or branched chain alkyl.

Preferred is where R₁ is OR where R is a C₁₋₂₀ straight or branchedalkyl, preferably methyl; R₂ is H; and R₃ is a C₁₋₂₀ straight orbranched chain alkyl, more preferably, butyl.

Examples of suitable UVA sunscreen compounds of this general formulainclude 4-methyldibenzoylmethane, 2-methyldibenzoylmethane,4-isopropyldibenzoylmethane, 4-tert-butyldibenzoylmethane,2,4-dimethyldibenzoylmethane, 2,5-dimethyldibenzoylmethane,4,4′diisopropylbenzoylmethane, 4-tert-butyl-4′-methoxydibenzoylmethane,4,4′-diisopropylbenzoylmethane,2-methyl-5-isopropyl-4′-methoxydibenzoymethane,2-methyl-5-tert-butyl-4′-methoxydibenzoylmethane, and so on.Particularly preferred is 4-tert-butyl-4′-methoxydibenzoylmethane, alsoreferred to as Avobenzone. Avobenzone is commercial available fromGivaudan-Roure under the trademark Parsol 1789, and Merck & Co. underthe tradename Eusolex 9020.

Other types of UVA sunscreens include dicamphor sulfonic acidderivatives, such as ecamsule, a sunscreen sold under the trade nameMexoryl™, which is terephthalylidene dicamphor sulfonic acid, having theformula:

The composition may contain from about 0.001-20%, preferably 0.005-5%,more preferably about 0.005-3% by weight of the composition of UVAsunscreen. In the preferred embodiment of the invention the UVAsunscreen is Avobenzone, and it is present at not greater than about 3%by weight of the total composition.

2. UVB Chemical Sunscreens

The term “UVB sunscreen” means a compound that blocks UV radiation inthe wavelength range of from about 290 to 320 nm. A variety of UVBchemical sunscreens exist including alpha-cyano-beta,beta-diphenylacrylic acid esters as set forth in U.S. Pat. No. 3,215,724, which ishereby incorporated by reference in its entirety. One particular exampleof an alpha-cyano-beta,beta-diphenyl acrylic acid ester is Octocrylene,which is 2-ethylhexyl 2-cyano-3,3-diphenylacrylate. In certain cases thecomposition may contain no more than about 110% by weight of the totalcomposition of octocrylene. Suitable amounts range from about 0.001-10%by weight. Octocrylene may be purchased from BASF under the tradenameUvinul N-539.

Other suitable sunscreens include benzylidene camphor derivatives as setforth in U.S. Pat. No. 3,781,417, which is hereby incorporated byreference in its entirety. Such benzylidene camphor derivatives have thegeneral formula:

wherein R is p-tolyl or styryl, preferably styryl. Particularlypreferred is 4-methylbenzylidene camphor, which is a lipid soluble UVBsunscreen compound sold under the tradename Eusolex 6300 by Merck.

Also suitable are cinnamate derivatives having the general formula:

wherein R and R₁ are each independently a C₁₋₂₀ straight or branchedchain alkyl. Preferred is where R is methyl and R₁ is a branched chainC₁₋₁₀, preferably C₈ alkyl. The preferred compound is ethylhexylmethoxycinnamate, also referred to as Octoxinate or octylmethoxycinnamate. The compound may be purchased from GivaudanCorporation under the tradename Parsol MCX, or BASF under the tradenameUvinul MC 80. Also suitable are mono-, di-, and triethanolaminederivatives of such methoxy cinnamates including diethanolaminemethoxycinnamate. Cinoxate, the aromatic ether derivative of the abovecompound is also acceptable. If present, the Cinoxate should be found atno more than about 3% by weight of the total composition.

Also suitable as UVB screening agents are various benzophenonederivatives having the general formula:

wherein R through R₉ are each independently H, OH, NaO₃S, SO₃H, SO₃Na,Cl, R″, OR″ where R″ is C₁₋₂₀ straight or branched chain alkyl Examplesof such compounds include Benzophenone 1, 2, 3, 4, 5, 6, 7, 8, 9, 10,11, and 12. Particularly preferred is where the benzophenone derivativeis Benzophenone 3 (also referred to as Oxybenzone), Benzophenone 4 (alsoreferred to as Sulisobenzone), Benzophenone 5 (Sulisobenzone Sodium),and the like. Most preferred is Benzophenone 3.

Also suitable are certain menthyl salicylate derivatives having thegeneral formula:

wherein R₁, R₂, R₃, and R₄ are each independently H, OH, NH₂, or C₁₋₂₀straight or branched chain alkyl. Particularly preferred is where R₁,R₂, and R₃ are methyl and R₄ is hydroxyl or NH₂, the compound having thename homomenthyl salicylate (also known as Homosalate) or menthylanthranilate. Homosalate is available commercially from Merck under thetradename Eusolex HMS and menthyl anthranilate is commercially availablefrom Haarmann & Reimer under the tradename Heliopan. If present, theHomosalate should be found at no more than about 15% by weight of thetotal composition.

Various amino benzoic acid derivatives are suitable UVB absorbersincluding those having the general formula:

wherein R₁, R₂, and R₃ are each independently H, C₁₋₂₀ straight orbranched chain alkyl which may be substituted with one or more hydroxygroups. Particularly preferred is wherein R₁ is H or C₁₋₈ straight orbranched alkyl, and R₂ and R₃ are H, or C₁₋₈ straight or branched chainalkyl. Particularly preferred are PABA, ethyl hexyl dimethyl PABA(Padimate O), ethyldihydroxypropyl PABA, and the like. If presentPadimate O should be found at no more than about 8% by weight of thetotal composition.

Salicylate derivatives are also acceptable UVB absorbers. Such compoundshave the general formula: wherein R is a straight or branched chainalkyl, including derivatives of the above compound formed from mono-,di-, or triethanolamines. Particular preferred are octyl salicylate,TEA-salicylate, DEA-salicylate, and mixtures thereof.

Generally, the amount of the UVB chemical sunscreen present may rangefrom about 0.001-45%, preferably 0.005-40%, more preferably about0.01-35% by weight of the total composition.

If desired, the compositions of the invention may be formulated to havea certain SPF (sun protective factor) values ranging from about 1-100,preferably about from about 10 to 75 with ratios of UVA and UVB rangingfrom 1-3:1.

F. Film Formers

It may be desired to incorporate one or more film formers into thecompositions of the invention. Film formers will generally enhance thefilm formed by the cosmetic applied to the skin and, in some cases,promote water resistance or transfer resistance. If present, such filmformers may range from about 0.1 to 50%, preferably from about 0.5 to40%, more preferably from about 1 to 35% by weight of the totalcomposition.

Suitable film formers may be based on silicone or organic polymers.Particularly preferred are crosslinked silicone resins generallyreferred to as MT or MQ resins. Examples of such resins include the MQresin trimethylsiloxysilicate or an MT resin calledpolymethylsilsesquioxane. Trimethylsiloxysilicate may be purchased fromDow Corning under the tradename 749 Fluid which is about a 50/50 mixtureof trimethylsiloxysilicate and cyclomethicone, or General Electric underthe tradename SR1000. Polymethylsilsesquioxane may be purchased fromWacker-Chemie under the tradename MK resin.

The composition may contain other ingredients including preservatives,botanical extracts, vitamins, antioxidants, and the like.

IV. The Method and Product

The invention is directed to a method for imparting color to keratinoussurfaces while improving the appearance of dimensionality, depth, orundertones of the surface through application of a compositioncomprising composite particulates having a portion comprised of at leastone colorant and a portion comprised of at least one clear ortranslucent thermoplastic material to the skin.

It has been found that if at least some portion of the total colorantcomponent present in the composition is replaced with compositeparticulates, the color applied to skin provides a more naturalappearance with depth and dimensionality, while allowing the naturalundertones of the skin to show through. The composition may be in theform of foundations, blushes, eyeshadow, and the like. Preferably, whenabout 0.1-99%, preferably 10-90% of the total colorant component isreplaced with composite particulates, optimized coverage and improvedappearance will result.

The invention is also directed to a method for reducing the ashy,chalky, or mask-like appearance of a cosmetic composition on skin byapplying a composition wherein at least a portion of the total colorcomponent has been replaced with composite particulates. Generally whenfrom about 0.1-99%, preferably 10-90% of the total colorant component isreplaced with composite particulates the ashy, chalky or mask-likeappearance of the composition is reduced when applied to the skin.

The invention is also directed to a method for reducing the number ofstock keeping units in a color cosmetic shade range and the resultingcolor cosmetic shade range. The phrase “color cosmetic” means acomposition applied to a keratinous surface such as skin, hair, ornails, for the purpose of imparting color. Examples include foundationmakeup, blush, eye shadow, and the like with foundation makeup beingmost preferred. The term “shade range” means that range of shadesoffered by the cosmetics manufacturer for one particular SKU of thecolor cosmetic. By way of example, foundation makeup “Product X” has SKUno. 1234 which identifies Product X, and has 25 different color shades,the shade codes designated by two digit numbers, e.g. 01 through 25,that is, 1234-01, etc. Or in another example, a blush-on “Product Y” isidentified by SKU no. 4567 and has six different color shades in theline, the shade codes designated by two digit numbers, e.g. 01 through06.

In the method of the invention, the number of shades in the shade rangefor color cosmetics such as foundation makeup, blush-on, and the likemay be reduced from 10 to 80% by using the composite particulates toformulate the color cosmetic composition. In formulating the cosmeticcompositions, the composite particulates may be substituted for 100% ofthe total colorant component of the composition. Alternatively, thecomposite particulates may be substituted for a portion of the colorantcomponent. For example, shade reduction is achieved in the preferredembodiment of the invention when about 30-80%, more preferably fromabout 40-60% of the total colorant component is replaced with compositeparticulates. Other suitable ranges may be from about 0.1-99% preferablyfrom about 20-80%, more preferably from about 30-70% by weight of thetotal colorant component is replaced with composite particulates.

In one embodiment, the method provides for a foundation makeup shaderange that exhibits a 10-60% reduction in the number of shades. Moreparticularly, the invention provides for a foundation makeup productline having an original shade range comprised of 15 to 30 individualdifferent shades, wherein the number of shades in the shade range may bereduced from 0.1-99%, preferably from about 10-90% when the foundationsare formulated with composite particulates as described herein. In thepreferred embodiment as exemplified, the original foundation makeup linehad 19 shades. When the foundation formula was prepared wherein fromabout 40-60% of the total colorant component was replaced with compositeparticulates, it was possible to reduce the number of shades to 11 andstill match all of the skin colors in the same shades as were matchedwith the 19 shades, thus a reduction of 42% in the number of shades.

The invention will be further described in connection with the followingexamples which are set forth for the purposes of illustration only.

Example 1

A color blend was made by first mixing 50/50 ratio of 250 grams ofspherical Polymethylmethacrylate (PMMA) particles (Microsphere M-100,Tomen America; or Sepimat P from SEPPIC) and 250 grams red iron oxide(Unipure Red LC 381EM, Sensient Technologies, South Plainfield, N.J.) atroom temperature in a lab scale CBM mixing container (Model LabmasterHC-1A, Teledyne Special Equipment, Readco Products, York, Pa.) having arotating blade or impellor that spins at about 7,000 rpm with a tumblespeed set at 35 rpm and at a process run time of 2 minutes. At roomtemperature under a fume hood, 250 grams of the color was added to astainless steel beaker and diluted with 625 grams of acetone withpropeller agitation suitable for mixing without splashing. The mixturewas allowed to remain in the beaker until it formed a consistency ofpourable thick syrup, about 3 to 5 minutes. The beaker contents werepoured into a Pyrex-type glass baking dish and spread to a uniformthickness of about 0.25 to 0.5 inches. The mixture was allowed to dryfor 24-36 hours or until the color blend was hard and brittle and freefrom acetone odor.

The dried color blend was removed as a single sheet from the glass dishand broken up into smaller pieces with gloved hands to a size suitablefor hammer milling through a 0.20 inch screen.

The color blend pieces were then passed through a hammer mill (RetschCorporation, Model SR300, Haan Germany) with 0.02 inch screen so thatthe pieces were reduced to reduce to a particle size suitable for jetmilling (generally about 600 microns or less).

The color blend particles were then jet milled using a Model 4 jet millsupplied by Sturtevant, Inc., 348 Circuit Street, Hanover, Mass. The airinlet pressure was set at 105 psi and the grinding pressure at 100 psi.The material feed rate was set at 40 grams per minute. The milling wasperformed at room temperature for 1 hour. After grinding of the colorblend particles they were collected for spray drying.

After jet milling the color blend particles were sieved to remove anylarge particles (e.g. those greater than 45 microns) prior to spraydrying using a lab scale model Octagon Ce Digital vibrating sievemachine (Endicotts Limited, Lombard Road, London SW19 England). Thecolor blend particles that passed through the 45 micron sieve werecollected for spray drying. The color blend particles that did not passthrough the sieve were discarded.

The color blend particles that passed through the sieve were then coatedin a spray drying machine (Glatt Model GPCG-1 Spray Drying Unit, GlattTechnologies, Inc.). The unit was loaded with from about 500 grams to 1kilogram of the color blend particles. The machine was set with thefollowing parameters: Interval Filter Shaker—vibration set at 5 secondintervals; Exhaust Air Flap—set at 0.4 bar; Atomization SprayPressure—set at 2.5 bar; Liquid Spray Flow Rate set at 25 ml per minute.To 500 grams of color blend particles was added 94.09 grams of DowCorning 7-4404 Fluid (a mixture of about 35-45 parts trisiloxane andabout 40-70 parts dimethicone silylate), which was spray dried onto thecolor blend particles. This yielded a powder blend with about 7% byweight of the coated color blend particles. After completion of spraydrying the particles were collected and dried overnight in an oven(Cascade TEK Model VO-2) at a temperature of 70-80° C.

A final sieve step was performed after spray drying to removeagglomerates. The spray dried coated color blend particles were sievedas set forth above through the 45 micron screen. The resulting coatedcolor blend particles were free flowing and had an average particle sizeof about 10 microns.

The process set forth herein was repeated with yellow iron oxide(Unipure Yellow LC 182 EM, Sensient Cosmetic Technologies), black ironoxide (Unipure Black LC 989 EM, Sensient Cosmetic Technologies), andtitanium dioxide (AFDC 200, Kemora Pigments Oy, Finland). The resultingspray dried coated composite yellow iron oxide particles had a particlesize of about 15 microns. The resulting spray dried coated color blendblack iron oxides had a particle size of about 10.6 microns; the rediron oxide composite particles about 15 microns; and the titaniumdioxide composite particles about 15 microns. The composition of thecomposite particulates was:

Thermo- % By plastic % By % By Color Colorant Weight Material WeightCoating Weight White TiO₂ 46.5 PMMA 46.5 trisiloxane 7 dimethiconesilylate Red Red iron oxides 46.5 PMMA 46.5 trisiloxane 7 dimethiconesilylate Black Black iron oxides 46.5 PMMA 46.5 trisiloxane 7dimethicone silylate Yellow Yellow iron oxides 46.5 PMMA 46.5trisiloxane 7 dimethicone silylate

The resulting composite particulates were used to prepare foundationmakeup compositions.

Example 2

Foundation makeup compositions were made as follows:

% By Weight Ingredient Formula 1(M) Formula 2Cyclopentasiloxane/PEG/PPG-18/18 5.00 5.00 Dimethicone (90:10) Sorbitansesquioleate 0.20 0.20 Cyclopentasiloxane 19.67 19.67 PEG-10 Dimethicone3.25 3.25 Lecithin 0.001 0.001 Pentaerythrityl tetra-di-t-butyl 0.050.05 hydroxyhydrocinnamate Titanium dioxide/triethyoxycaprylylsilane7.21 3.61 Yellow iron oxides/triethoxycaprylylsilane 2.42 1.21 Red ironoxides/triethoxycaprylylsilane 0.65 0.32 Black ironoxides/triethxycaprylylsilane 0.22 0.11 Silica/titaniumdioxide/dimethicone 0.02 — Titanium dioxide — 3.63 Invention compositecolorant (yellow iron — 6.87 oxides/red iron oxides, silica/black ironoxides/PMMA/trisiloxane, dimethicone silylate) 14:32:1:71:11Silica/titanium dioxide/dimethicone — 0.02 Hydrogenated lecithin 0.100.10 Silica/methoxyamodimethicone/ 1.00 — silsesquioxane copolymerTitanium dioxide/triethoxycaprylylsilane 1.04 1.04Trimethylsiloxysilicate 2.50 2.50 Tocopheryl acetate 0.05 0.05Cyclopentasiloxane/disteardimonium 2.25 hectorite/propylene carbonate(75/20/5) Cyclomethicone/dimethicone/PEG-10 2.50 2.50 crosspolymer (KSG24) Cyclomethicone/dimethicone crosspolymer 3.50 3.50Dimethicone/dimethicone/PEG10/15 3.50 2.50 crosspolymerEthylhexylmethxycinnamate 2.50 2.50 Water QS100 QS100 Butylene glycol3.00 4.00 Sorbic acid 0.20 0.20 Phenoxyethanol/chloroxylenol 1.00 1.00Xanthan gum 0.20 0.20 Laureth-7 0.25 0.25 Magnesium sulfate 1.50 1.50Hyaluronic acid (1% aqueous solution) 2.00 2.00

The compositions were prepared by combining the water phase and oilphase ingredients and mixing well to emulsify. The resulting foundationswere water in oil emulsions.

Example 3

Formula 1 and Formula 2 were tested on 30 female panelists as follows:

-   -   ranging in age from 18 to 55 years,    -   normal to oily skin types,    -   users of department store or prestige brand liquid foundation,    -   used the foundation at least five days a week; and    -   preferred full to full-to-medium coverage and a natural finish.

A five day unidentified crossover study was performed and at thebeginning all of the panelists were shade acceptors of the test shade.The term “unidentified” means that the panelists were not aware of whatcosmetics company was conducting the test. The term “crossover” meansthat the panelists were divided into two groups of 15. The term“acceptors of the test shade” means that each of the panelists found thetest shade of the foundation to be acceptable. Each group of 15 testedthe first of the test foundations for two days. On day 3 the panelistsreturned to the test site and were given the second test foundation forthe last two days of the study.

The panelists were provided with the foundation of Formula 1 or Formula2 in a glass jar labeled “foundation”, and instructed to apply thefoundation daily after their skin care regimen and in place of theirusual foundation by blending over the face. Panelists were instructednot to introduce any new products into their makeup or skin care regimenduring the test period. Panelists completed a self-administeredquestionnaire after each two day usage period and direct comparisonquestions were asked at the conclusion of the study.

Panelists were asked which foundation, Formula 1 or Formula 2 theypreferred when compared to the normally used foundation. The resultswere as follows:

Formula 2 Comparison Formula 1 (invention) No. panelists that likedmuch/somewhat 23 22 more/same as regularly used foundation No. paneliststhat liked much/somewhat more 10 12 than regularly used foundation No.panelists that liked much more then 2 4 regularly used foundation No.panelists who liked much/somewhat less 7 8 than regularly usedfoundation

Example 4

Eleven additional foundation makeup compositions according to theinvention were made as follows from the composite particulates preparedin Example 1:

% By Ingredient Weight Deionized water QS100 Cyclopentasiloxane 19.17Cyclopentasiloxane/PEG/PPG-18/18 dimethicone 5.00 Total compositeParticulates ** Titanium dioxide/triethoxycaprylylsilane 4.24Cyclomethicone/dimethicone crosspolymer 3.50 PEG-10 dimethicone 3.25Butylene glycol 3.00 Ethylhexyl methoxycinnamate 2.50Cyclopentasiloxane/dimethicone/PEG-10 crosspolymer 3.50Dimethicone/dimethicone/PEG-10/15 crosspolymer 2.50 Magnesium sulfate1.50 Cyclopentasiloxane/disteardimonium hectorite/propylene 1.13carbonate Titanium dioxide/triethoxycaprylylsilane 1.04Phenoxyethanol/chloroxylenol 1.00 Yellow ironoxides/triethoxycaprylylsilane 0.85Silica/methoxyamodimethicone/silsesquioxane copolymer 0.50 Laureth-70.25 Sorbitan sesquioleate 0.20 Sorbic acid 0.20 Xanthan gum 0.20 Rediron oxides/triethoxycaprylylsilane 0.13 Hydrogenated lecithin 0.10Tocopheryl acetate 0.05 Pentaerythrityl tetra-di-t-butylhydroxyhdrocinnamate 0.05 Black iron oxides/triethoxycaprylylsilane 0.03Sodium hyaluronate 0.02 Silica/titanium dioxide/methicone 0.02Phenoxyethanol 0.02

The amount of composite particulates in % by weight of the totalformulas SG1-11 were as follows:

SG1 SG2 SG3 SG4 SG5 SG6 SG7 SG8 SG9 SG10 SG11 W 8.48 7.61 7.25 7.17 5.745.13 2.72 1.61 1.51 1.44 1.86 B 0.07 0.12 2.57 0.21 0.21 0.34 0.42 1.151.35 2.43 2.09 R 0.26 0.34 0.48 0.49 0.69 0.98 2.56 1.68 2.08 2.56 2.34Y 1.69 2.43 0.20 2.63 3.86 4.05 4.80 6.06 5.56 4.07 4.21 ** 10.5 10.510.5 10.5 10.5 10.5 10.5 10.5 10.5 10.5 10.5 Total Compositeparticulate: W = white, B = black, R = red, Y = yellow.

Example 5

A study with 200 panelists was conducted to determine whether foundationmakeup containing the inventive technology provided improved universalshade matching sufficient to match a variety of skin shades in one shadecategory and thus contribute to SKU reduction.

200 panelists were recruited. A professional makeup artist selected afoundation from the MAC Studio Fix Fluid SPF15 foundation makeup line(commercially available) that matched the skin color of each of thepanelists. The shades of the MAC Studio Fix foundation were as follows:

Shade Category Shade Numbers of MAC studio Fix Fluid SPF15 Light NC15,NW15 Light/Medium NC20, NW20, NC25, NW25, NC30 Medium NC35, NC37, NW30,NC40, NC42 Medium/Dark NC44, NW35, NW40, NW43, NC45 Dark NW45, NC50,NW47 Deep/Dark NW50, NW55, NC55

The ingredient list on the MAC Studio Fix Fluid SPF 15 foundations thatwere used read as follows:

ACTIVE INGREDIENTS: OCTINOXATE 2.50% [ ] TITANIUM DIOXIDE 1.00%INGREDIENTS: WATER\AQUA\EAU [ ] CYCLOPENTASILOXANE [ ] PEG-10DIMETHICONE [ ] BUTYLENE GLYCOL [ ] TRIMETHYLSILOXYSILICATE [ ]DIMETHICONE [ ] MAGNESIUM SULFATE [ ] DIMETHICONE/PEG-10/15 CROSSPOLYMER[ ] LAMINARIA SACCHARINA EXTRACT [ ] ALGAE EXTRACT [ ] TOCOPHERYLACETATE [ ] SODIUM HYALURONATE [ ] TOCOPHEROL [ ] LECITHIN [ ]HYDROGENATED LECITHIN [ ] XANTHAN GUM [ ] SORBITAN SESQUIOLEATE [ ]METHOXY AMODIMETHICONE/SILSESQUIOXANE COPOLYMER [ ] LAURETH-7 [ ]PEG/PPG-18/18 DIMETHICONE [ ] DISTEARDIMONIUM HECTORITE [ ] SILICA [ ]DIMETHICONE CROSSPOLYMER [ ] TRIETHOXYCAPRYLYLSILANE [ ] PROPYLENECARBONATE [ ] PENTAERYTHRITYL TETRA-DI-T-BUTYL HYDROXYHYDROCINNAMATE [ ]SORBIC ACID [ ] CHLOROXYLENOL [ ] PHENOXYETHANOL [ ] [+/−TITANIUMDIOXIDE (CI 77891) [ ] IRON OXIDES (CI 77491, CI 77492, CI 77499) [ ]CHROMIUM OXIDE GREENS (CI 77288)]

The shade of the Studio Fix product that most matched the skin of eachpanelist was selected by the professional makeup artist and applied toeach of the panelists. Both the professional makeup artist and panelistagreed that the color applied matched the skin.

The MAC Studio Fix foundation was then removed from the skin of thepanelist and the professional makeup artist selected a foundation fromSG1 through SG11 shades and applied to each of the panelists. Uponconclusion of the application both the professional makeup artist andthe panelist agreed that the foundation applied matched the skin.

The results showed that the foundations in SG1 through SG11 (11 shades)matched all of the skin shades reflected in the entire shade line (19shades) for the MAC Studio Fix products, thus resulting in a:

MAC Matching SG Shade Studio Fix Shades Category Shades (invention)Comments Light NC15, NW15 SG1 The single SG1 shade matched both NC15 andNW15 shades of MAC Studio Fix foundation in the Light shade category.Light NC20, NW20, SG2, SG3 Two shades, SG2 and SG3, Medium NC25, NW25,matched five shades of MAC NC30 Studio Fix foundation in theLight/Medium shade category. SG2 matched NC20, NW20, NC25. SG3 matchedNW25, NC30. Medium NC35, NC37, SG4, SG5 Two shades, SG4 and SG5, NW30,NC40, matched five shades of MAC NC42 Studio Fix foundation in theMedium shade category. SG4 matched NC35, NC37, NW30. SG5 matched NC40,NC42. Medium NC44, NW35, SG6, SG7 Two shades, SG6 and SG7, Dark NW40,NW43, matched five shades of MAC NC45 Studio Fix foundation in theMedium/Dark shade category. SG6 matched NC44, NW35, NW40. SG7 matchedNW43, NC45. Dark NW45, NC50, SG8, SG9 Two shades, SG8 and SG9, NW47matched three shades of MAC Studio Fix foundation in the Dark shadecategory. SG8 matched NW45, NC50. SG9 matched NW45, NW50, NW47. DeepNW50, NW55, SG10, SG11 Two shades, SG10 and SG11, Dark NC55 matchedthree shades of MAC Studio Fix foundation in the Deep Dark shadecategory. SG10 matched NW50, NW55. SG11 matched NW50, NW55, NC55.

The above results are depicted in the FIG. 1 attached hereto, anddemonstrate that foundation compositions containing the compositeparticulates of the invention are significantly more universal inmatching foundation shades thus contributing to SKU reduction. Inparticular, it was possible to reduce the number of shades to 11 fromthe original 19 by using the composite particulates of the invention forformulate the foundation composition.

Example 6

A composite particulate in the collapsed microsphere form was preparedusing Expancel 551 DE 20 d 60 (DE 20 stands for average particle size of20 microns). About 800 grams was placed into a mixing chamber. Acetonein an amount of about 4,000 mL was added under 20 RPM. A gel was formedand about 343 g of ultra fine titanium dioxide (D 50 2 microns) wasadded to the gel. The combination of titanium dioxide and the gel wasmixed until homogeneous. The acetone was removed by heating thecombination in a vacuum chamber. The titanium dioxide particles wereentrapped in the microspheres and the outer layer of the microsphereover-coated with about 14 percent by weight of a Dow Corning 1107silicone polymer. The final particle size of the TiO₂-entrappingmicrospheres was measured using a Malvern Particle Size Analyzer,available from Malvern Instrument Scirocco 2000 at Worcestershire, UKand the result was between 5 to 8 microns.

Example 7

A composite particulate in the collapsed microsphere form is preparedusing Expancel 551 DE 20 d 60 (DE 20 stands for average particle size of20 microns). About 800 grams is placed into a mixing chamber. Acetone inan amount of about 4,000 mL is added under 20 RPM. A gel is formed andabout 343 g of ultra fine titanium dioxide (D 50 2 microns) is added tothe gel. The combination of red iron oxides and the gel is mixed untilhomogeneous. The acetone is removed by heating the combination in avacuum chamber. The red iron oxide particles are entrapped in themicrospheres and the outer layer of the microsphere over-coated withabout 14 percent by weight of a Dow Corning 1107 silicone polymer. Thefinal particle size of the TiO₂-entrapping microspheres is measuredusing a Malvern Particle Size Analyzer, available from MalvernInstrument Scirocco 2000 at Worcestershire, UK and the result is between5 to 8 microns.

Example 8

1 kg of spherical PMMA particles (Sepimat P from SEPPIC) and 1 kg rediron oxide (Unipure Red LC 381EM, Sensient Technologies, SouthPlainfield, N.J.) were put into an anti-static bag (Anti-Static Bags,Champion Plastics, 220 Clifton Blvd, Clifton, N.J.) and placed into a 50gallon drum that was rotated at 68 rpm on the drum roller (Morse, EastSyracuse, N.Y.) for about 1 hour. The blend was removed from the drumand placed in a LittleFord DVT Polyphase Reactor with 5 gallon innervolume (LittleFord Day Inc., Florence, Ky.) and heated to 72° C. whilemixing at the tip speed of blades 0.3-0.5 ft/s. In a separate vessel,1.42 kg ethanol (Reagent alcohol 200 proof anhydrous—Grade ACS, SigmaAldrich) was heated to 72° C. and added to the LittleFord unit. Thegelled material was mixed until uniform by mixing at the tip speed ofblades 0.3-0.5 ft/s. The ethanol was removed by vacuum and heating to75° C. Dry powder was hammer milled with 0.01 inch screen in a HosokawaHammermill 1 HP (Hosokawa Col, Osaka Japan). To 2 kg of color blendparticles was added 376.36 grams of Dow Corning 7-44-4 Cosmetic Fluid (amixture of about 35-45 parts trisiloxane and about 4-70 partsdimethicone silylate) and mixed in the LittleFord unit until uniform.

The system was treated by heat at 75° C. under vacuum and nitrogenstream until dry. This yielded a powder blend with about 7% by weight ofthe coated color blend particles. A final hammermill step was performedafter drying to remove agglomerates.

The above process above was repeated using yellow iron oxide (UnipureYellow LC 182 EM, Sensient Cosmetic Technologies), black iron oxide(Unipure Black LC 989 EM, Sensient Cosmetic Technologies) and titaniumdioxide (AFDC 200, Kemore Pigments, Oy Finland). The resulting driedyellow iron oxide-containing particles had a particle size of about 8microns. The resulting dried coated black iron oxide-containingparticles had a particle size of about 8 microns. The red ironoxide-containing particles had a particle size of about 8 microns. Thecomposition of the composite particles was as set forth below:

Colorant PMMA Coating* Composite % By Weight % By Weight % By WeightParticulate Colorant in Composite in Composite in Composite Color UsedParticulate Particulate Particulate White TiO₂ 46.5 46.5 7 Red red ironoxide 46.5 46.5 7 Black black iron oxide 46.5 46.5 7 Yellow yellow ironixide 46.5 46.5 7 *Trisiloxane/dimethicone silylate

Example 9

A lipstick composition is prepared as follows:

Ingredient w/w % Aloe barbadensis extract/mineral oil 0.50Trimethylsiloxyphenyl dimethicone (PDM 1000) 1.00 Octyldodecyl stearoylstearate 3.05 Ceresin wax 6.50 Petrolatum 32.05 Hydrogenated vegetableoils 14.00 Polybutene 0.25 Ozokerite 16.25 Ethylhexyl methoxycinnamate7.50 Propyl paraben 0.15 Phenyl trimethicone 1.00 Bis-diglycerylpolyacyladipate 2.50 Cetyl esters QS Ethylhexyl salicylate 3.50Tocopheryl acetate 0.25 Example 8 Pigments 4.00

The composition is prepared by grinding the pigments in a portion of thecetyl esters. The waxes and oils were separately combined with heat andmixed well. The pigment grind was added to the mixture and stirred well.The mixture is poured into molds and allowed to cool to roomtemperature.

Example 10

Powder eyeshadow and blush compositions are prepared as follows:

w/w % Ingredient Shadow Blush Aluminum hydroxide 0.003 Sorbitansesquioleate 0.001 Ascorbyl palmitate 0.04 Barium sulfate 0.0005 Soybeanextract 2.47 BHT 0.70 0.05 Lecithin 0.0004 Candelilla wax 5.85 Carnauba1.76 Castor seed oil QS Polyglyceryl-3 beeswax 3.23 Simethicone 0.05Dipentaerythrityl hexahydroxystearate 2.50 Isodecyl neopentanoate 0.05Caprylic/capric triglycerides 9.90 Mica 4.75 Oleyl oleate 6.70 Octylpalmitate 7.00 Polybutene QS Hydrogenated polyisobutene 30.13 Dextrinpalmitate 11.00 Ozokerite 2.35 Synthetic wax 4.95 Diisostearyl malate8.70 Bis-diglyceryl polyacyladipate-2 1.47 Polydecene 2.10 0.35Mica/titanium dioxide 0.80 Propyl paraben 0.10 Titanium dioxide 3.10Tocopheryl acetate 0.04 Iron oxides 5.11 FD&C blue no. 1 aluminum lake0.10 0.002 D&D Red No. 6 0.01 D&C Red No. 7 Calcium Lake 0.36 0.25Fragrance 0.50 Example 8 pigment blend 1.00 1.15

The compositions are prepared by grinding the pigments in a portion ofthe oil. Separately, the oils and waxes were combined with heat andmixed well. The pigment grind is added. The compositions are pressedinto pans.

Example 11

Oil in water emulsion mascara compositions are prepared as follows:

Ingredients w/w % Water QS100 QS100 QS100 Butylene glycol 5.00 3.00 3.00Ethylhexyl glycerin 0.30 Water/acrylates copolymer 10.00 Polyglyceryl-3diisostearate liquid 0.50 Iron oxides 6.00 3.00 3.00 Example 8 pigmentblend 6.00 3.00 3.00 Kaolin powder 4.00 3.00 6.00 Polyisobutene 6.00Acrylates/octylacrylamide copolymer 5.00 Methyl methacrylatecrosspolymer dispersion 6.00 9.00 Mica 2.00 Mica/Methyl methacrylatecrosspolymer 3.00 Silica 1.00 Polyquaternium-10 0.70Steareth-100/Disteareth-100 IPDI copolymer 1.00 3.00 2.25 viscous liquidPolyimide-1 12.00 Sodium polystyrene sulfonate (FF polymer) 6.00Simethicone (liquid) 0.10 0.10 0.10 Biosaccharide gum (skin conditioningagent) 0.10 Sodium dehydroacetate 0.10 0.10 0.10 Bentonite (thickeningagent) 1.25 1.25 Disodium EDTA (preservative) 0.10 0.10 0.10Hydrogenated castor oil (solid) 5.00 Steareth-2 (solid) 2.25 Steareth-21(solid) 0.75 3.50 3.50 PEG-6 decyltetradeceth-30 0.50 PEG-40hydrogenated castor oil (solid) 0.50 Ricinus Communic (Castor) seed oil(Liquid) 2.00 PEG-20 (Solid) 2.00 3.00 3.00 PVP 0.50 PTFE 2.00 Polyvinylalcohol (Film forming polymer) 3.00 3.00 Nylon 6/silica 0.50Water/hydrolyzed wheat protein/PVP 1.00 crosspolymer Water/hydrolyzedwheat protein 1.00 Water/hydrolyzed wheat protein/cystine 7.00bis-PG-propyl silanetriol copolymer (skin conditioning agetnt)Water/polyaminopropyl biguanide 0.20 0.10 0.05 Water/acrylatescopolymer, butylene 5.00 glycol/sodium laureth sulfatePhenoxyethanol/caprylyl glycol/potassium 0.75 sorbate/water/hexyleneglycol Phenoxyethanol 0.40 0.40 Phenoxyethanol/caprylyl glycol/potassium0.85 sorbate/water/hexylene glycol Aminomethyl propanediol 0.05

The composition is prepared by combining the water phase and oil phaseingredients separately, then mixing the phases to emulsify and form amascara composition.

While the invention has been described in connection with the preferredembodiment, it is not intended to limit the scope of the invention tothe particular form set forth but, on the contrary, it is intended tocover such alternatives, modifications, and equivalents as may beincluded within the spirit and scope of the invention as defined by theappended claims.

What is claimed is:
 1. A color cosmetic composition containing a totalcolorant component consisting of (a) 30 to 80 parts of compositeparticulates consisting of a fused agglomerate of 40-60% colorant and60-40% of a clear or translucent thermoplastic Polymethylmethacrylate(PMMA) having a refractive index ranging from 1.1 to 1.6, a meltingpoint of 50 to 200° C. and a density ranging from about 0.5 to 5grams/cm³, and (b) 70 to 30 parts of colorant not in compositeparticulate form wherein said fused agglomerate is not in the form of acollapsed microsphere, wherein said fused agglomerate is made by thesteps of: (a) solvating the clear or translucent thermoplastic PMMA inthe form of solid spheres with a solvent; (b) combing the solvatedmixture of (a) with one or more colorants; (C) removing the solvent toform a fused agglomerate.
 2. The composition of claim 1 wherein thecolorant in the composite particulate is a powder, or a pigment that isan organic pigment, an inorganic pigment, or mixtures thereof.
 3. Thecomposition of claim 2 wherein the organic pigment in the compositeparticulate is a D&C color, FD&C color, or Lake thereof and theinorganic pigment is one or more iron oxides, titanium dioxide, or zincoxide.
 4. The composition of claim 1 wherein the colorant in thecomposite particulate is a white or non-colored particulate.
 5. Anemulsion foundation makeup containing the color composition of claim 1.6. The composition of claim 1 wherein the composite particulates arecoated with an ingredient selected from silicone elastomers, siliconeresins, silicone gums, synthetic waxes, natural waxes, and mixturesthereof.
 7. The composition of claim 1 wherein the composite particulateis coated with dimethicone silylate.
 8. The composition of claim 5 whichis in the water in oil emulsion form and further comprisescyclopentasiloxane, dimethicone, dimethicone crosspolymer, and PEG-10crosspolymer.